CN108779344A

CN108779344A - Method for manufacturing the product containing white pigment

Info

Publication number: CN108779344A
Application number: CN201780015783.2A
Authority: CN
Inventors: J·索特曼; J·A·麦尔
Original assignee: Omya Development AG
Current assignee: Omya Development AG
Priority date: 2016-02-16
Filing date: 2017-02-13
Publication date: 2018-11-09
Anticipated expiration: 2037-02-13
Also published as: US20190233652A1; EP3208314B1; CO2018009654A2; JP2019511586A; CN108779344B; EP3417013B1; ES2801750T3; EP3417013A1; US11168218B2; CA3013984A1; KR20180110082A; EP3417013B8; WO2017140630A1; EP3208314A1

Abstract

The present invention relates to a kind of methods for manufacturing the product containing white pigment.The product containing white pigment is obtained by froth flotation from least one material containing white pigment and impurity.

Description

Method for manufacturing the product containing white pigment

The present invention relates to a kind of methods for manufacturing the product containing white pigment, and relate more specifically in order to logical Froth flotation separation white pigment and impurity are crossed for manufacturing the technical field implemented containing the product of white pigment.

Pigment is typically considered changes the material of the color of reflected light or transmitted light since wavelength selectivity absorbs.This Physical process is different from shining for fluorescence, phosphorescence and other forms, wherein material Emission.Pigment be used for for example painting, ink, Plastics, fabric, cosmetics, food and other materials are coloured.The most of pigment used are dry colorants, are usually milled into Fine powder.

Due to its industrial relevance, white pigment occupies special status in field of pigments.For example, the paper maker in Europe In industry, the annual white pigment using more than 10,000,000 tons.White pigment is also used in paint and coating.Especially in manufacture point When dissipating property paint, white pigment is the primary colours in tinting system.

Naturally occurring white pigment is usually obtained by digging up mine.Cause to change colour however, usual such white pigment contains The impurity of (such as graying or flavescence).In addition, these impurity may influence the characteristic of white pigment, and therefore in its use In lead to notable disadvantage.A large amount of impurity (silicate such as in white pigment) may increase abrasive characteristic.Therefore, it is necessary to Impurity and white pigment are separated from each other with obtain not by or the product containing white pigment that is only small amount easily polluted by the external foreign matters.

It is well known in the art that impurity is detached from white mineral by physical-chemical separation.Physical-chemical detaches Process is related to mill first metamorphic rock or sedimentary rock, and then by the material containing white pigment and impurity of gained aqueous Usual foam flotation is subjected in environment.Usual foam flotation is the method for highly versatile well known in the prior art, is used for base The energy of particular surface is selectively adhered in comprising the aqueous suspension containing white pigment and the material of impurity in bubble The difference of power detaches to carry out the physical-chemical of particle.Then it takes the bubble for being attached with white pigment to surface and takes out, together When keep complete wetting impurity retain in the liquid phase.

As described above, the basis of usual foam flotation is the difference of the wetability of white pigment and impurity.White pigment can To be native hydrophobic, but usually hydrophobicity is induced by being chemically treated.Surface is set to have hydrophobic chemical treatment main It is the method with one layer of suitable compound coated particle surface.

However, conventional flotation have the shortcomings that it is notable：As mentioned earlier, as the chemical treatment of collecting agent is for making white face The surface of material has hydrophobicity to detach these particles by gas sparging.These adsorption of collector are on the surface of white pigment On, and therefore change the characteristic of pigment.However, this changes in the following with may be undesirable on the way of white pigment： In paper, plastics, paint, coating, concrete, cement, cosmetics, water process, food, pharmacy, ink and/or agricultural application, Wherein the product containing white pigment is preferably used in wet-end process, cigarette paper, cardboard and/or the coating application of paper machine, Or as rotogravure printing and/or offset printing and/or ink jet printing and/or continuous ink jet printing and/or aniline printing and/or electricity Son photograph and/or ostentatious support.Further, since quality and economic cause, the direct flotation of required white pigment are Unfavorable.

Alternatively, it is contemplated that detach white pigment and impurity using anti-/ indirect froth flotation.It is floating compared to conventional Choosing, wherein desirable white pigment is directly floated and collected from the foam of generation, anti-(indirect) flotation is intended to make not conforming to The impurity needed is preferentially floated and is removed, to leave the suspension concentrated relative to desirable white pigment. During reverse flotation, also using make impurity have hydrophobic collecting agent.

The use of the corresponding method of collecting agent is known in anti-froth flotation, a kind of collecting agent is ester based quaternary ammonium salt.

US 3,990,966 is related to a kind of wet method for purifying calcite ore, passes through following progress：It mills Calcite ore and the slurry for forming calcite ore, by the presence of flotation agent from wherein flotation impurity come from calcite The impurity is detached in slurry, classifies to the calcite slurry of gained, the calcite of classification is deposited in thickener simultaneously And desciccate.As flotation agent, cationic surfactant is selected from the group being made up of：(a) 17 carbon of 1- ethoxys -2- Alkenyl glyoxide, (b) salt derivative of 1- ethoxys -2- alkyl imidazolines and (c) described imidazoline, the wherein alkyl of imidazoline Part is the moieties of the aliphatic acid with certain length so that the surfactant is used as liquid.

CA 1 187 212 is related to a kind of method purifying the carbonate ore containing silicate by flotation, wherein will Ore is subjected to being milled to the fineness for being enough to discharge impurity.Collecting agent is the cationoid reaction selected from the group being made of following quaternary ammonium Object：A) dimethyl dialkyl with 8 to 16 carbon atoms in alkyl, the alkyl is saturation or the insatiable hunger of linear chain or branched chain The aliphatic series of sum；B) dimethyl alkyl benzyl with 10 to 22 carbon atoms in group alkyl, the alkyl is linear aliphatic； C) bi-imidazoline containing 12 to 18 carbon atoms in alkyl, the alkyl are the saturated or unsaturated aliphatic series of straight chain；d) Derived from quaternary ammonium a), salt b) and c).

2008/084391 A1 of WO are related to a kind of for purifying the method for wrapping minerals calciferous comprising at least One flotation step, it is characterised in that this step uses at least one season imidazoline metilsulfate compound as collecting agent.

2008/089906 A1 of WO are related to a kind of method for flotation unsulfided minerals or ore, wherein will pressure Broken rough substance or ore is mixed with water and collecting agent to form suspension.In reagent system and wherein formed containing described The buoyant foam body of unsulfided minerals or ore in the presence of the flotation residue comprising gangue together with introducing air into It, can be by by alkanolamine and unitary carboxylic wherein it includes using polymer esters quaternary ammonium salt as collecting agent to improve in suspension The mixture of acid and dicarboxylic acids reacts and makes the ester of gained quaternized next in a known way optionally after alkoxylate It obtains.

2011/147855 A2 of WO are related to polymer season ester products in foam flotation method as the purposes of collecting agent, It is related to a kind of method for carrying out froth flotation using polymer season ester, is related to such polymer season ester, and be related to using In the method for production polymer season ester.

WO2010/051895 A1 are related to A) include at least one organic group and optionally for being attached to amino nitrogen atom Including hetero atom and with 1 to 36 carbon atom at least one quaternary ammonium compound and B) formula (1) at least one amine alkoxy The composition of ester or its salt using 10 to the amount of 5000g/ tons of ore as the purposes of the collecting agent in silicate flotation, wherein A, B be independently of one another C2 to C5 alkylidenes R1, independently of one another C8 to C24 alkyl or alkenyls R2, R3, R4, H or C8 to C24 acyl Base is, it is specified that at least one of group R2, R3 or R4 represent C8 to C24 acyl groups, and x, y, z represents 0 to 50 independently of one another Integer, it is specified that x+y+z is 1 to 100 integer.

2 659 028 A1 of EP are related to by the product that following reaction obtains to be used as to be inhibited for the corrosion of metal surface The purposes of agent：The mixture of aliphatic acid with formula R1COOH (I) or acid, and the dicarboxylic acids with formula (IIa) or (IIb) or its Derivative with formula (III) alkoxylated fats amine or part thereof or completely quaternary ammonium derivative react；Optionally, exist Described react between aliphatic acid, dicarboxylic acids and alkoxylated fats amine carries out further reaction step, which part later Or whole nitrogen-atoms is quaternized by being reacted with alkylating agent R5X.

US 5,720,873 is related to a kind of method of calcium carbonate mineral of the cleaning containing silicate impurity, wherein froth flotation Method executes in the presence of specific cation-collecting agent.

What 2167883 A of AU were related to realizing in the water-bearing media containing fuel oil collecting agent and conditioning agent determines size The froth flotation of coal, the conditioning agent include by by the aliphatic acid or aliphatic acid of 1 mole of alkanolamine (I) and >=0.8mol The acid derivative of product or this product that ester condensation is formed.

00/62937 A1 of WO are related to a kind of foam flotation method, and wherein silicate is in catching containing specific quaternary ammonium compound It is detached from iron ore in the presence of receipts agent.This collecting agent for the concentrate silicate in foam product have it is highly selective, And the iron mineral matter of high yield is maintained in one or more concentrates of bottom.

97/26995 A1 of WO are related to purposes of the so-called season ester as the auxiliary agent for non-sulfide ore substance flotation.

US 4,995,965 is related to a kind of for removing silicate impurity from ore to purify calcium carbonate by reverse flotation The method of ore.The method realizes that the high yield of calcium carbonate product and low acid non-soluble substance contain by using specific collecting agent Amount.

101337204 A of CN are related to diquaternary ammonium compound in silicate mineral flotation and in bauxite or iron ores The specific collecting agent of specific diquaternary ammonium compound is applied in stone Counterfloatating desiliconization.

101816981 A of CN are related to a kind of specific environmental-friendly amine cation collecting agent and its application method.

1 584 674 A1 of EP are related to a kind of ester quat concentration being suitable for production fabric softener at a lower temperature Object, the Ester Quat Concentrate include a) ester quats compounds；B) organic solvent；C) water；D) pH adjusting agent.

1 806 392 A1 of EP are related to the aqueous combination of the mixture containing specific ester quat or specific ester quat Object.

1 876 224 A1 of EP are related to a kind of stabilization, uniform and sticky softening agent, contain less than 50 weight % Specific ester quats compounds.

2005/0189113 A1 of US are related to including the acid of acidic fluid and ester-containing quaternary ammonium compound (" ester quat ") Property treatment fluid and its application method.

2 700 680 A1 of EP are related to a kind of method for manufacturing the product containing white pigment.Contain white pigment Product froth flotation carried out by using specific collecting agent obtain from least one material containing white pigment and impurity.

US 4,606,916 be related to by with dicarboxylic acids polycondensation and then with alkylene oxide and carboxylic acid or inorganic acid or and season Ammonium agent such as methyl chloride reacts the specific season alkoxylate polyester prepared by alkoxylated fats amine.The compound is suitble to use Make cosmetic active compound, is specifically used for the cosmetics nursing of hair.

0 035 263 A2 of EP are related to specific fabric softener, are the polyester containing tertiary amino or itself and rudimentary carboxylic The salt of sour (such as acetic acid or glycolic) and inorganic acid.

However, for there are multiple shortcomings come the art methods for manufacturing product by anti-froth flotation.Using such Collecting agent is very expensive.In addition, many known collecting agents lead to uncontrolled foaming in anti-foam flotation method.This Outside, many anti-foam flotation methods are restricted, because they are selective, i.e. the signal portion Yu impurity one of required product Play floating.The a large amount of collecting agents used so far are also considered as aquatic and environmental toxicity.Known collecting agent it is another It is a the disadvantage is that they decomposed under flotation conditions and therefore lose efficiency.

Therefore, it is necessary to it is a kind of for by flotation production white pigment improved method, the method avoid or reduce with The upper problem related with known method.It is this to be used for from the material manufacture white pigment containing white pigment and impurity Improved method especially should be easily handled and ecology method.Effect is also answered satisfactory.

The present invention has been resolved at least some foregoing purposes.

According to an aspect of the present invention, a kind of method for manufacturing the product containing white pigment, feature are provided It is the described method comprises the following steps：

A) at least one material containing white pigment and impurity is provided；

B) collecting agent for the group that at least one selects the compound of free style (1) to form is provided

R¹Selected from the group being made up of：

I) direct key,

ii)C₁-C₂₀The saturation or aliphatic unsaturated hydrocarbon of linear chain or branched chain, the hydrocarbon chain is optionally by one or more-OH bases Group, one or more methyl and/or methylene group, cycloalkylene group, sub- cycloalkenyl groups and/or arylene group take Generation, preferably

A) the alkylidene group with 1 to 20, more preferably 1 to 10 carbon atom, the alkylidene most preferably replaced Group, wherein the substituted alkylidene group is by 1 or 2-OH group, 1 or 2 methyl and/or methylene group, sub- cycloalkanes Base group, sub- cycloalkenyl groups and/or arylene group substitution, or

B) the alkenylene group with 1 to 20, preferably 1 to 10 carbon atom, the alkenylene base more preferably replaced Group, wherein the substituted alkenylene group is by 1 or 2-OH group, 1 or 2 methyl and/or methylene group, cycloalkylidene Group, sub- cycloalkenyl groups and/or arylene group substitution；

R²Selected from by hydrocarbyl group or formula R with 8 to 24 carbon atoms⁴-O-(A′O)_wThe group of the group composition of-T-, In；

R⁴Indicate the hydrocarbyl group with 8 to 24 carbon atoms；

W is number in the range of 0 to 20；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 6 carbon atom；

R³Selected from the group being made of hydrocarbyl group or benzyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms；

X indicates to be derived from alkylating agent R³The anion of X；

X is number in the range of 1 to 20；

P is number in the range of 1 to 15；

T is 0 or 1；

Y is 0 or 1；And

The group of G expressions (2)；

Wherein；

B indicate alkyl with 1 to 4 carbon atoms group or

Indicate benzyl group；

S is 1,2 or 3；

R³, X and t it is as defined above；

N⁺The R being connected in formula (1)²；And

(CH₂)_sThe quaternary nitrogen atoms being connected in formula (1)；

C) by the collecting agent of the material containing white pigment and impurity of step a) and step b) containing water ring Mixing is to form aqueous suspension in border；

D) gas is passed through into the suspension of the formation in step c)；

E) by taking out in the aqueous suspension that obtains after the step d) mutually described contain is recycled with white pigment There is the product of white pigment.

Inventor is it was unexpectedly observed that for from least one material containing white pigment and impurity and according to formula (1) The method of at least one product of the collecting agent manufacture containing white pigment

It is advantageous, because compared to the surface for being attached to white pigment, above-mentioned collecting agent is much more effectively attached to The surface of impurity.In addition, collecting agent according to the present invention shows high stability and is not decomposed largely under flotation conditions.

Therefore, compared with known art methods, property method for floating of the invention is very effective.In addition, this The method for floating of invention is very ecological, because compared with the collecting agent of the known prior art, collecting agent toxicity used It is smaller.The product containing white pigment obtained by the method for the present invention shows good brightness and has low yellow colour index.

The second aspect of the present invention is related to the phase with white pigment of the acquisition of method through the invention in paper, modeling Purposes in material, paint, coating, concrete, cement, cosmetics, water process, food, pharmacy, ink and/or agricultural application.Contain The product of white pigment is preferably used in wet-end process, cigarette paper, cardboard and/or the coating application of paper machine, or as wheel Turn intaglio printing and/or offset printing and/or ink jet printing and/or continuous ink jet printing and/or aniline printing and/or electrofax And/or ostentatious support.

The Favourable implementations of the present invention are defined in corresponding dependent claims.

According to an embodiment, the method is related to indirect flotation step, results in foam and tool containing impurity There is the phase with white pigment of the product containing white pigment.

According to another embodiment, white pigment is white mineral matter pigment, is preferably chosen from the group being made up of： Natural whiting or powdered whiting, packet mineral material calciferous, dolomite, barite, aluminium oxide, titanium dioxide with And the mixture of aforementioned substances.

According to another embodiment, white mineral matter pigment is alkaline earth metal carbonate, preferably calcium carbonate and Most preferably powdered whiting (GCC).

According to another embodiment, the material containing white pigment includes the impurity selected from the group being made up of：Sulphur Change iron, iron oxide, graphite, silicate and its mixture.Silicate can be selected from the group being made up of：Quartz, mica, angle are dodged Rock, feldspar, clay mineral and its mixture, and preferably quartz.

According to another embodiment, silicate is the silicate of the color white selected from the group being made up of：Silicon ash Stone, kaolin, kaolinite clay, the kaolinite clay of calcining, montmorillonite, talcum, diatomite, sepiolite and its mixture.

According to another embodiment, the amount of the white pigment in the material containing white pigment and impurity of step a) is The 0.1 weight % based on dry weight to 99.9 weight %, based on dry weight preferably 30 weight % are to 99.7 weight %, more preferably 60 weight % are to 99.3 weight %, and most preferably 80 weight % to 99 weight %.

According to another embodiment, white pigment in the material containing white pigment and impurity of step a):Impurity Ratio is 0.1 based on dry weight:99.9 to 99.9:0.1, preferably 30 based on dry weight:70 to 99.7:0.3, more preferably 60:40 to 99.3:0.7, and most preferably 80:20 to 99:1.

According to another embodiment, the weight median particle of the material containing white pigment and impurity of step a) is 1 To 1 000 μm, preferably 3 to 700 μm, more preferably 5 to 500 μm and most preferably 10 to 80 μm or 100 to 400 μm of model In enclosing.

According to another embodiment, the compound of formula (1) characterizes as follows：

R¹Indicate the alkylidene group with 2 to 6 carbon atoms, more preferably 4 carbon atoms；

R²Indicate hydrocarbyl group or formula R with 12 to 24 carbon atoms⁴-O-(A′O)_wThe group of-T-；Wherein

R⁴Indicate the hydrocarbyl group with 12 to 24 carbon atoms；

W is number in the range of 0 to 10, preferably 0 to 3；

A ' O indicate the polyoxyalkylene group with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 4 carbon atom, preferably with 2 to 3 carbon atoms；

R³Indicate alkyl with 1 to 4 carbon atoms group；

X indicates halogen, sulfate radical or carbonate；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms, preferably with 2 carbon atoms；

X is number in the range of 1 to 10；Number more preferably in the range of 1 to 6；And

P is number in the range of 1 to 10, preferably in the range of 1 to 5.

According to another embodiment, as the compound provided in step b) selects the compound of free style (1a) to form Group：

Wherein,

AO、p、t、x R¹、R²、R³With X as defined in the first embodiment, preferably such as in previous embodiment It is defined.

According to another embodiment, the compound of formula (1a) characterizes as follows：

R¹It indicates with 1 to 20, preferably 1 to 10 carbon atom, preferably with 2 to 6 carbon atoms and more excellent Selection of land has the alkylidene group of 4 carbon atoms；

R²Indicate the hydrocarbyl group with 8 to 24 carbon atoms, preferably with 12 to 24 carbon atoms；

R³Indicate the hydrocarbyl group with 1 to 4 carbon atom, the preferably alkyl group with 1 or 2 carbon atom simultaneously And more preferably methyl group；

AO is polyoxyalkylene group, preferably ethoxy group；

X is to be derived from alkylating agent R³The anion of X；Preferably chlorion or sulfate radical；

X is in the range of 1 to 15, preferably in the range of 2 to 10 and more preferably in the range of 1 to 6 Number；

P is number in the range of 1 to 15；And

T is 0 or 1, preferably 1.

According to another embodiment, the compound of formula (1a) possesses at least one of following characteristics：

R¹Derived from dicarboxylic acids, dicarboxylic acid chloride, the diester of dicarboxylic acids, dicarboxylic acids acid anhydrides, preferably R¹Derivative is free The compound of free group consisting of：Oxalic acid, malonic acid, succinic acid, glutaric acid, glutaconate, adipic acid, muconic acid, heptan Diacid, phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, malic acid, maleic acid, fumaric acid, suberic acid, mesaconic acid, Decanedioic acid, azelaic acid, tartaric acid, itaconic acid, glutinicacid, citraconic acid, brassylic acid, dodecanedioic acid, traumatic acid, it is general Sour, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or acid anhydrides and its mixture, more preferably R¹It is derived from Compound selected from the group being made up of：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, O-phthalic Acid, tetrahydrophthalic acid, malic acid, tartaric acid, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or acid anhydrides And its mixture, and most preferably adipic acid；；

R²Derived from the fatty amine selected from the group being made up of：2 ethyl hexylamine, 2- propyl heptyl amice, n-octyl amine, the positive last of the ten Heavenly stems Amine, n-dodecane amine, (Cocoalkyl)-amine, (palm oil alkyl) amine, n-tetradecane base amine, n-hexadecyl amine, n-octadecane Base amine, oleyl amine, (tallow alkyl)-amine, (hydrogenated tallow alkyl)-amine, (rapeseed alkyl)-amine, (soya alkyl)-amine, erucic acid Amine, N- (positive decyl)-N- methyl-trimethylenes-diamines, N- (dodecyl)-N- methyl-trimethylenes-diamines, N- (coconut palms Oily alkyl)-N- methyl-trimethylenes-diamines, N- (rapeseed alkyl)-N- methyl-trimethylenes-diamines, N- (soybean alkane Base)-N- methyl-trimethylenes-diamines, N- (tallow alkyl)-N- methyl-trimethylenes-diamines, N- (hydrogenated tallow alkyl)- N- methyl-trimethylenes-diamines, N- (erucic acid)-N- methyl-trimethylenes-diamines, isotridecyl oxygen propylamine and its mixing Object, preferably (Cocoalkyl)-amine or (tallow alkyl)-amine；

R³Derived from the alkylating agent selected from the group being made up of：Dimethyl suflfate, dithyl sulfate, carbonic acid diformazan Ester, benzyl chloride, methyl bromide, methyl chloride, methyl iodide, preferably dimethyl suflfate or methyl chloride and its mixture.

According to another embodiment, the compound of formula (1a) possesses following characteristics：

R¹Derived from the compound selected from the group being made up of：Adipic acid, maleic anhydride, decanedioic acid and glutaric acid；

R²Derived from the ethoxylated fatty amine selected from the group being made up of：Ethoxylation (C₁₆-C₁₈) and C₁₈Insatiable hunger With alkylamine, ethoxylation (C₈-C₁₆) and C₁₈Unsaturated alkyl amine, ethoxylation (Cocoalkyl)-amine, ethoxylation oil base Amine, ethoxylation (tallow alkyl)-amine and ethoxylation (palm oil alkyl)-amine；And

R³Derived from the alkylating agent selected from the group being made up of：Dimethyl suflfate, dithyl sulfate and methyl chloride, and And preferably methyl chloride.

According to another embodiment, the collecting agent of step b) is by formula (1) and/or one or more compound groups of (1a) At.

According to another embodiment, the aqueous suspension obtained in step c) has 7 to 10, preferably 7.5 to 9.5 And more preferably 8.5 to 9 pH.

According to another embodiment, collecting agent is added with amount below in step c)：Containing based on step a) is white 1 to 5 000ppm of the gross dry weight of the material of color pigment and impurity, preferably amount are described containing white face based on step a) 20 to 2 000ppm of the gross dry weight of the material of material and impurity, more preferably amount is 30 to 1 000ppm, and is most preferably measured It is 50 to 800ppm.

According to another embodiment, the aqueous suspension obtained in step c) has based on the solid in suspension Solid content between the 5 weight % and 80 weight % of total weight, preferably 10 of the total weight based on the solid in suspension Between weight % and 70 weight %, between more preferably 20 weight % and 60 weight % and most preferably 25 weight % and 55 weights Measure the solid content between %.

According to another embodiment, one or more additives are added to before, during or after step c) and are contained Water slurry, wherein additive are selected from the group being made up of：PH adjusting agent, solvent, inhibitor, polyelectrolyte, foaming agent with And the collecting agent other than according to the collecting agent of formula (1) and/or (1a).

According to another embodiment, during and/or after the aqueous suspension that is obtained in step c) is in step c) into Row is milled.

According to another embodiment, the gas in step d) is air.

According to another embodiment, the suspension in step d) have between 5 DEG C and 40 DEG C, preferably at 10 DEG C and Between 40 DEG C, more preferably between the 10 DEG C and 30 DEG C and most preferably temperature between 15 DEG C and 25 DEG C.

According to another embodiment, the phase with white pigment that is obtained from step e) step e) before and/or it After disperseed and/or milled, and preferably in the presence of at least one dispersant and/or at least one mill auxiliary agent into Row disperses and/or mills.

According to another embodiment, the product containing white pigment includes at least white of 95 weight % based on dry weight Pigment, preferably at least 98 weight %, more preferably at least 99 weight % and most preferably at least 99.9 weights based on dry weight Measure the white pigment of %.

According to another embodiment, a kind of method for manufacturing the product containing white pigment is provided, feature exists In the described method comprises the following steps：

A) at least one material containing white pigment and impurity is provided；

B) collecting agent for the group that at least one selects the compound of free style (1) to form is provided：

R¹Selected from the group being made up of：Direct key, the alkylidene group with 1 to 10 carbon atom, substituted alkylene Base group, wherein the alkylidene group is by 1 or 2-OH group, cycloalkylene group, sub- cycloalkenyl groups and arlydene base Group's substitution；

R⁴Indicate the hydrocarbyl group with 8 to 24 carbon atoms；

W is number in the range of 0 to 20；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 6 carbon atom；

R³Selected from the group being made of hydrocarbyl group or benzyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms；

X indicates to be derived from alkylating agent R³The anion of X；

X is number in the range of 1 to 20；

P is number in the range of 1 to 15；

T is 0 or 1；

Y is 0 or 1；And

The group of G expressions (2)；

Wherein；

B indicate alkyl with 1 to 4 carbon atoms group or

Indicate benzyl group；

S is 1,2 or 3；

R³, X and t it is as defined above；

N⁺The R being connected in formula (1)²；And

(CH₂)_sThe quaternary nitrogen atoms being connected in formula (1)；

D) gas is passed through into the suspension of the formation in step c)；

" pigment " in the meaning of the present invention is that the solid with the chemical composition and characteristic crystal structure that limit Color material.Pigment can be inorganic pigment.Pigment can be synthesis or natural pigment.In addition, pigment is not soluble in water and therefore Suspension is generated when contacting it with water.

" white pigment " in the meaning of the present invention is by the pigment with white appearance when solar radiation.

" white mineral matter pigment " in the meaning of the present invention is the inorganic white pigment that can naturally obtain, and specific Ground includes natural whiting or powdered whiting (especially lime stone, chalk, marble, calcite), packet mine calciferous Material (can be with the CaCO of the minimum 70 weight % contents of the weight based on minerals₃), dolomite, barite, oxidation The mixture of aluminium, titanium dioxide and aforementioned substances.

" alkaline earth metal carbonate " in the meaning of the present invention is the carbonic acid for including at least one alkaline earth metal cation Salt.Alkaline-earth metal according to the present invention is beryllium Be²⁺, magnesium Mg²⁺, calcium Ca²⁺, strontium Sr²⁺, barium Ba²⁺And radium Ra²⁺。

" calcium carbonate " in the meaning of the present invention includes natural whiting, and can be powdered whiting (GCC).

" natural whiting " in the meaning of the present invention is obtained from natural origin such as marble, lime stone or chalk Calcium carbonate (calcite).

" powdered whiting " (GCC) in the meaning of the present invention is such as to be milled, sieved by wet method and/or dry process Divide and/or be fractionated the natural whiting of (such as passing through cyclone separator or clasfficiator progress).In the meaning of the present invention " miscellaneous Matter " is the substance different from the chemical composition of required white pigment.

" collecting agent " in the meaning of the present invention is the granular absorption being conceived to by chemisorption or physisorption Chemical compound.Collecting agent makes contaminant surface have more hydrophobicity.

" gas " in the meaning of the present invention is to conform to the shape for the container that gas is held therein in and holding The object of uniform density (or even in the presence of gravity and so and regardless of the amount of the substance in container) is obtained in device The sample of matter.If being not limited to container, gaseous material (also referred to as steam) will be distributed in space.Term gas referring also to The state or condition of the substance of this characteristic use.Gas is made of the molecule in constant random motion.According to the present invention, change Object is closed under room temperature (20 DEG C ± 2 DEG C) and necessarily is in gaseous state under standard atmospheric pressure (101 325Pa or 1.01325 bars).

The undissolved solid and appoint that " suspension " or " slurry " in the meaning of the present invention is included in water-bearing media The other additive of selection of land, and a large amount of solids are usually contained, therefore more viscosity and comparable aqueous Jie for supporting suspension Matter has higher density.

Fine (i.e. d herein₅₀<5 μm) " granularity " of the material containing white pigment and impurity pass through its granularity point Cloth d_xTo describe.Wherein, value d_xIt indicates that the x weight % relative to its particle has and is less than d_xDiameter diameter.It means that For example, d₂₀Value is certain granularity, and 20 weight % of whole particles are less than this granularity.Therefore d₅₀Value is Weight Median Particle Size, i.e., 50 weight % of whole crystal grain are more than this granularity and remaining 50 weight % is less than this granularity.For purposes of the present invention, it removes Non- other instruction, otherwise fine (i.e. d₅₀<5 μm) granularity of the material containing white pigment and impurity is designated as Weight Median Granularity d₅₀。d₉₈Value is certain granularity, and 98 weight % of whole particles are less than this granularity.By using Micromeritics The SedigraphTM 5100 or 5120 instruments of Instrument companies determines fine granulation (i.e. d₅₀<5μm).The method and Instrument is known to technical staff, and commonly used in determining the granularity of filler and pigment.In 0.1 weight %Na₄P₂O₇It is water-soluble Implement to measure in liquid.Sample is disperseed and is ultrasonically treated using high speed agitator.

(the i.e. d of coarse grain herein₅₀Higher than 5 μm) " granularity " of the material containing white pigment and impurity pass through its grain Degree distribution d_xTo describe.Wherein, value d_xIt indicates that the x weight % relative to its particle has and is less than d_xDiameter diameter.This meaning It, for example, d₂₀Value is certain granularity, and 20 weight % of whole particles are less than this granularity.Therefore d₅₀Value is Weight Median grain 50 weight % of degree, i.e., whole crystal grain are more than this granularity and remaining 50 weight % is less than this granularity.For the mesh of the present invention , unless otherwise instructed, otherwise (the i.e. d of coarse grain₅₀>5 μm) granularity of the material containing white pigment and impurity is designated to attach most importance to Measure median particle d₅₀。d₉₈Value is certain granularity, and 98 weight % of whole particles are less than this granularity.By using from Britain 2000 laser diffraction systems of Malvern Mastersizer of Malvern companies determine coarseness (i.e. d₅₀>5μm).It uses Mie is theoretical, in the iRI (absorption index) and Malvern application software of the RI (particle refractive index) and 0.005 of 1.57 definition Analysis is by measuring the initial data obtained in the case of 5.60.Water-dispersible body executes measurement.For this purpose, using high speed Blender dispersed sample.If the equal density of all particles, the size distribution that weight determines can correspond to volume determination Granularity.

" specific surface area (SSA) " of calcium carbonate product in the meaning of the present invention is defined as the solid of blocky drying sample The quality of surface area (distribution for representing all existing particles) divided by bulk sample.As used herein, specific surface area uses BET Thermoisopleth (ISO 9277:2010) it is measured by adsorbing and is indicated with m2/g.

" conventional flotation method " or " direct flotation method " in the meaning of the present invention is a kind of method for floating, wherein closing The white pigment needed is directly floated and is collected from the foam of generation, to leave the suspension containing impurity.

" reverse flotation method " or " indirect flotation method " in the meaning of the present invention is a kind of method for floating, wherein impurity It directly floats and is collected from the foam of generation, leave the suspension containing required white pigment.

The method of the present invention for manufacturing the product containing white pigment is related to providing at least one " containing white pigment With the material of impurity " and at least one present invention collecting agent.The material containing white pigment and impurity and the collecting Agent mixes in aqueous environment to form aqueous suspension.After blending or mixing periods, gas is contained by what is obtained Water slurry, and after by gas by suspension, by taking out the phase with white pigment back and forth from aqueous suspension Receive the product containing white pigment.

Hereinafter, the details of the method for manufacturing the product containing white pigment and preferred reality will be described in greater detail Apply scheme.It should be understood that these embodiments or details be also applied for the acquisition of method through the invention containing white pigment Product and be also applied for also can be through the invention the purposes of the invention of the phase with white pigment that obtains of method.

Material containing white pigment and impurity

The step a) of the method for the present invention refers to providing at least one minerals for including white pigment and impurity.

White pigment in the meaning of the present invention is the pigment with white appearance when being observed in daylight.White pigment White property be based primarily upon the visible light that relatively low light absorption is incorporated at pigment-Air Interface non-selective light dissipate It penetrates.White pigment according to the present invention is the inorganic white pigment that can be naturally obtained with synthesis, and includes specifically natural carbon Sour calcium or powdered whiting (especially lime stone, chalk, marble, calcite), packet mineral material calciferous (can have There is the CaCO of the minimum 50 weight % contents of the weight based on minerals₃), dolomite, barite, aluminium oxide, titanium dioxide with And the mixture of aforementioned substances.

White pigment can be white mineral matter pigment.White mineral matter pigment in the meaning of the present invention is can be natural The inorganic white pigment of acquisition.Except above-mentioned natural whiting or powdered whiting (especially lime stone, chalk, Dali Stone, calcite), packet mineral material calciferous (can be with the minimum 50 weight % contents of the weight based on minerals CaCO₃), dolomite, barite and aforementioned substances mixture other than, white mineral matter pigment includes containing aluminium oxide Al₂O₃ Minerals, such as γ-Al with cubic structure₂O₃With the α-Al with rhombohedron (triangle) structure₂O₃.In addition, containing There are the minerals of aluminium oxide to may include other elements, such as Na₂O·11Al₂O₃(commonly referred to as diaoyudaoite (diaoyudaoit)) sodium in.The white mineral matter pigment of other present invention is containing titanium dioxide TiO₂Minerals, example Such as rutile, anatase or brockite.Other white mineral matter pigment is oxide white minerals such as barium sulfate (BaSO₄), zinc oxide (ZnO), zirconium dioxide (ZrO₂) or stannic oxide (SnO₂), or white sulfate mineral matter and white sulphur Compound minerals such as zinc sulphide (ZnS) or ceruse (PbCO₃)。

Preferably, white mineral matter pigment is alkaline earth metal carbonate.

Alkaline earth metal carbonate in the meaning of the present invention is the carbonate for including at least one alkaline earth metal cation. Alkaline-earth metal according to the present invention is beryllium Be²⁺, magnesium Mg²⁺, calcium Ca²⁺, strontium Sr²⁺, barium Ba²⁺And radium Ra²⁺, and preferably magnesium And calcium.Alkaline earth metal carbonate in the meaning of the present invention is such as beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate Or radium carbonate.

An embodiment according to the present invention, alkaline earth metal carbonate are only made of a kind of alkaline-earth metal such as calcium.It can Alternatively, alkaline earth metal carbonate can be made of the mixture of two kinds of alkaline-earth metal such as such as calcium and magnesium, and therefore, alkaline earth gold It can be miemite, such as dolomite to belong to carbonate.Alkaline earth metal carbonate may include two or more alkaline-earth metal Mixture.In addition, alkaline earth metal carbonate may include other cation, such as the sodium in such as gaylussite (sodium carbonate calcium).

White pigment may include more than one alkaline earth metal carbonate.For example, white pigment may include a kind of magnesium carbonate and A kind of calcium carbonate.Alternatively, white pigment can be only made of a kind of alkaline earth metal carbonate.

White pigment may include the mixture of two or more white mineral matter pigment.For example, white pigment may include A kind of alkaline earth metal carbonate and the inorganic white pigment selected from the group being made up of：Aluminium dioxide, titanium dioxide, sulfuric acid Barium, zinc oxide, zirconium dioxide or stannic oxide, white sulfate or sulfide minerals.

Preferably, alkaline earth metal carbonate can be calcium carbonate.

Calcium carbonate or natural whiting are understood to open from sedimentary rock such as lime stone or chalk or from rotten marble rock The naturally occurring form for the calcium carbonate adopted.Known calcium carbonate exists as the crystal polymorph of three types：Calcite, aragonite And vaterite.Calcite is most common crystal polymorph, it is considered to be most stable of calcium carbonate crystal form.It is less common Be aragonite, it have discrete or cluster needle orthorhombic crystalline structure.Vaterite is most rare calcium carbonate polycrystalline type object, and It is typically unstable.Calcium carbonate almost all is calcite polymorph, it is stated that it is triangle-diamond shape and represents most Stable calcium carbonate polycrystalline type object." source " of term calcium carbonate in the meaning of the present invention refers to obtaining calcium carbonate from it Naturally occurring mineral material.The source of calcium carbonate also may include other naturally occurring component, such as magnesium carbonate, oxidation Aluminium etc..

The source of calcium carbonate can be selected from or mixtures thereof marble, chalk, calcite, dolomite, lime stone.Preferably, The source of calcium carbonate can be selected from marble.

Preferably, alkaline earth metal carbonate can be powdered whiting (GCC).Powdered whiting (GCC) is understood to logical Cross dry method or alternatively wet milling calcium carbonate, then carry out subsequent drying steps to obtain.

In general, any conventional milling device can be used to implement for step of milling, for example, to refine mainly by with the second object Under conditions of the impact of body generates, i.e., in one or more below：Ball mill, rod mill, oscillating mill, roll crushing Known other of machine, centrifugation impact grinder, vertical type pearl-grinding machine, grater, needle mill, hammer-mill or technical staff such are set It is standby.In the case where the mineral powders containing calcium carbonate include the mineral material containing calcium carbonate of wet-milling, step of milling Can make it is spontaneous mill generation under conditions of and/or by other such processing known to horizontal ball milling and/or technical staff It executes.The mineral material containing calcium carbonate of thus obtained wet-treating milled can by well known method, such as It is dehydrated by filtering, centrifugation or forced evaporation before dehydration.Another dry step can such as spray in single step Implement in drying or at least two steps.

Preferably, white pigment can be only made of a kind of powdered whiting.Alternatively, white pigment can be by being selected from difference The mixture of two kinds of powdered whitings of the powdered whiting in source forms.White pigment also may include the weight selected from separate sources The mixture of two or more powdered whitings of matter calcium carbonate.For example, white pigment may include it is a kind of selected from dolomite GCC and one kind being selected from the marmorean GCC of calcite.In addition to GCC, white pigment may include other white mineral matter pigment.

Material containing white pigment and impurity contains white pigment and impurity as defined above.In the meaning of the present invention Impurity be the substance different from the chemical composition of white pigment, and be not therefore white pigment.

It is that there is such as grey, black, brown, red or Huang by the impurity removed or reduced according to the method for the present invention The compound of any other color of the white appearance of color or influence white pigment material.Alternatively, to be removed or reduction Therefore impurity negatively affects white pigment with white but with the physical characteristic different from white pigment.

According to preferred embodiment, material of the starting material for example containing white pigment and impurity may include selected from vulcanization The impurity of iron.

Iron sulfide or iron hydrosulphate in the meaning of the present invention is interpreted to embrace broad range of stoichiometric equation With the iron of different crystal structure and the chemical compound of sulphur.For example, iron sulfide can be iron sulfide (II) FeS (magnetic iron ore) or Magnetic iron ore Fe_1-xS, wherein x are 0 to 0.2.Iron sulfide can also be ferrous disulfide (II) FeS₂(pyrite or marcasite).Sulphur Change iron also containing the other elements other than iron and sulphur, such as example at mackinawite (Fe, Ni)_1+xNickel in S-shaped formula, Middle x is 0 to 0.1.

Impurity in material containing white pigment and impurity can also be iron sulfide.

Iron sulfide in the meaning of the present invention is understood to the chemical compound being made of iron and oxide.Iron sulfide packet Include such as iron oxide (II) FeO (also referred to as wustite), iron sulfide (I, III) Fe₃O₄(also referred to as magnetic iron ore) and iron sulfide (III)Fe₂O₃.Iron sulfide further includes iron hydroxide and iron oxyhydroxide, contains the other element in addition to iron and oxygen Hydrogen.Iron hydroxide includes such as iron hydroxide (II) Fe (OH)₂With iron hydroxide (III) Fe (OH)₃, also referred to as bernalite. Iron oxyhydroxide includes the alpha-feooh for the formation prism shape acicular crystal for being for example also referred to as goethite, is also referred to as lepidocrocite Form the γ-FeOOH of rhomboid crystal structure, the δ-FeOOH and water with hexagonal crystal of also referred to as six side's lepidocrocites Iron ore FeOOH0.4H₂O.Iron oxide also contains other element, such as example in the Fe of also referred to as Schwertmannite₈O₈(OH)₆ (SO₄)·nH₂The chlorine in sulphur or the also referred to as FeO (OH, Cl) of kaganeite in O.

Material containing white pigment and impurity may include the impurity selected from graphite.

Graphite in the meaning of the present invention is understood to the allotrope of carbon.There are three types of main Types for natural graphite： Crystallize flake graphite, amorphous graphite and blocky graphite.Flake graphite (or abbreviation flake graphite) is crystallized as the flat of separation Plate-like particles occur, and have hexagonal margin if not rupturing, and when ruptured, edge can be irregular or have an angle 's.Amorphous graphite as fine grained occur, and by the thermal metamorphism of coal (final stage of incoalation) generate and Sometimes referred to as meta-anthracite.In the industry, very thin flake graphite is sometimes referred to as amorphous.Blocky stone Ink (also referred to as texture graphite) occurs in fissure vein or fracture, and shows as fibrous or acicular crystal aggregation big Block plate commensal.

Alternatively, the impurity in material containing white pigment and impurity can be silicate.Silicate can be Toner or grinding agent.

Silicate or silicate mineral in the meaning of the present invention is interpreted to embrace the compound of silicon and oxygen.Separately Outside, silicate may include other ion, such as aluminium ion, magnesium ion, iron ion or calcium ion.Silicate and silicate mine Substance can be selected from nesosilicate, sorosilicate, cyclosilicate, inosilicate, phyllosilicate and tectosilicate and amorphous Silicate.Nesosilicate is wherein SiO₄Tetrahedron is detached and the silicate mineral adjacent with metal ion.Usually Known nesosilicate is zircon, willemite, olivine, mullite, forsterite, alumino-silicate or fayalite.Companion silicon Hydrochlorate is that have 2:The silicate mineral of the ditetrahedron group of the separation of 7 silicon and the ratio of oxygen.Commonly known companion silicon Hydrochlorate is ilvaite (ilavite), cacoclasite, allochite or kornerupine.Cyclosilicate is the SiO containing connection₄On four sides The ratio of the cyclosilicate of the ring of body, wherein silicon and oxygen is 1:3.Commonly known cyclosilicate is bentonite, beryl or electricity Gas stone.Inosilicate or chain silicate are that have for single-stranded 1:The SiO of 3 ratios₃Or for double-strand 4:The Si of 11 ratios₄O₁₁ The tetrahedral mutual chain of silicate silicate mineral.Commonly known inosilicate is enstatite, wollastonite, rose brightness Stone (rhodenite), diopside or amphibolite, such as example grunerite, cummingtonite, actinolite (actinolithe) or angle are dodged Stone.Phyllosilicate is formed with Si₂O₅Or 2:The sheet silicate of the tetrahedral parallel plate of silicate of 5 silica ratio.It is logical Often known phyllosilicate is clay mineral, such as talcum, kaolin, kaolinite clay, the kaolinite clay of calcining, more water Kaolin, dickite, vermiculite, nontronite, sepiolite or montmorillonite；Mica mineral, for example, biotite, muscovite, phlogopite, Rubellan or glauconite；Or chlorite minerals, such as clinochlore.Tectosilicate or framework silicates have SiO₂On four sides Body or 1:The silicate tetrahedron of the three-dimensional framework of 2 silica ratio.Commonly known tectosilicate is quartz mine substance, such as example Such as quartz, tridymite and cristobalite；Feldspar ore substance, such as such as potassium feldspar including orthoclase and microcline, including plagioclase The sodium or anorthite of stone, albite and andesine or scapolite and zeolite.Amorphous silicate is such as diatomite or opal (opale)。

Silicate can be selected from the group being made up of：Quartz, mica, amphibolite, feldspar, clay mineral and its mixing Object, and preferably can be quartz.

Special consideration should be given to for by white pigment and the impurity that is made of quartz and/or other silicate for the method for the present invention Separation.

Preferably, the impurity in material containing white pigment and impurity is only made of quartz.

Alternatively, one or more impurity in material containing white pigment and impurity may include the silicon with white Hydrochlorate.For example, impurity may include that silicate, such as wollastonite, kaolin, kaolinite clay, the kaolinite clay of calcining, illiteracy take off Soil, talcum, diatomite or sepiolite.In a preferred embodiment in accordance with this invention, impurity is by the silicate with white Composition, and it is highly preferred that impurity is made of only a kind of silicate of color white.For example, impurity can be only by wollastonite, kaolinite Soil, kaolinite clay, calcining kaolinitic clay, montmorillonite, talcum, diatomite or sepiolite composition.Flotation according to the present invention Method obtains and these impurity detached can be further processed and in suitably application.What method through the invention obtained Only the silicate containing color white and preferably only contain a kind of impurity of the silicate of color white can with containing white The identical mode of product of color pigment uses.

In a preferred embodiment, white pigment in the material containing white pigment and impurity of step a) Amount can be the 0.1 weight % based on dry weight to 99.9 weight %, the preferably 30 weight % to 99.7 weight % based on dry weight, More preferably 60 weight % are to 99.3 weight %, and most preferably 80 weight % to 99 weight %.

In another preferred embodiment, white pigment in the material containing white pigment and impurity of step a): The weight ratio of impurity can be 0.1 based on dry weight:99.9 to 99.9:0.1, preferably 30 based on dry weight:70 to 99.7: 0.3, more preferably 60:40 to 99.3:0.7, and most preferably 80:20 to 99:1.

The total amount of white pigment and impurity in the material containing white pigment and impurity of step a) can indicate relative to At least 90 weight % of the total weight of material containing white pigment and impurity, relative to the material containing white pigment and impurity Total weight preferably at least 95 weight %, more preferably at least 98 weight % and most preferably at least 99 weight %.

As previously mentioned, in a preferred embodiment, impurity in the material containing white pigment and impurity can be by Silicate forms.In this case, the white pigment and silicate in the material containing white pigment and impurity of step a) Total amount indicate at least 90 weight %, preferably at least 95 weights relative to the total weight containing white pigment and the material of impurity Measure %, more preferably at least 98 weight %, and most preferably at least 99 weight %.

Alternatively, the material containing white pigment and impurity can be made of white pigment and silicate.Preferably, contain The material of white pigment and impurity can be made of white pigment and quartz.Alternatively, the material containing white pigment and impurity It can be made of with the silicate of the color white selected from the group being made up of white pigment：Wollastonite, kaolin, kaolinite are viscous Soil, calcining kaolinitic clay, montmorillonite, talcum, diatomite or sepiolite.

The weight median particle of the material containing white pigment and impurity of step a) can 1 to 1000 μm, preferably 3 to In the range of 700 μm, more preferably 5 to 500 μm and most preferably 10 to 80 μm or 100 to 400 μm.

In another preferred embodiment, the Weight Median grain of the material containing white pigment and impurity of step a) Diameter can in the range of 1 to 1 000 μm, preferably 3 to 500 μm, more preferably 5 to 100 μm and most preferably 10 to 80 μm, If subsequent method for floating is standard method for floating.Standard method for floating in the meaning of the present invention is to mill And/or the method for floating executed after material of the classification containing white pigment and impurity.

In another preferred embodiment, the Weight Median grain of the material containing white pigment and impurity of step a) Diameter can be at 1 to 1 000 μm, preferably 10 to 700 μm, more preferably 50 to 500 μm and most preferably 100 to 400 μm of model In enclosing, if subsequent method for floating is coarse flotation method.Coarse flotation method in the meaning of the present invention be First of material containing white pigment and impurity, which is milled, recycles the interior method for floating executed.

Collecting agent

The step b) of the method for the present invention refers to providing at least one collecting agent.

Collecting agent in the meaning of the present invention is the change for the granular absorption being conceived to by chemisorption or physisorption Chemical combination object.

Collecting agent according to the present invention has general formula (1),

Wherein；

R¹Selected from the group being made up of：

I) direct key,

R³Indicate the hydrocarbyl group with 8 to 24 carbon atoms；

W is number in the range of 0 to 20；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 6 carbon atom；

R³Selected from the group being made of hydrocarbyl group or benzyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms；

X indicates to be derived from alkylating agent R⁴The anion of X；

X is number in the range of 1 to 20；

P is number in the range of 1 to 15；

T is 0 or 1；

Y is 0 or 1；And

The group of G expressions (2)；

Wherein；

B indicate alkyl with 1 to 4 carbon atoms group or

Indicate benzyl group；

S is 1,2 or 3；

R³, X and t it is as defined above；

N⁺The R being connected in formula (1)²；And

(CH₂)_sThe quaternary nitrogen atoms being connected in formula (1)；

In a preferred embodiment, it is the compound according to formula (1a) according to the compound of general formula (1).

Wherein, AO, p, t, x, R¹、R²、R³It is as defined above with X.

It should be understood that the nitrogen-atoms in formula (1) and (1a) has positive charge in t=1, but it is neutrality in t=0.

Formula (1) and the compound of (1a) can be prepared according to known technology of preparing.

For example, formula (1) and the compound of (1a) can be easy to through the dicarboxylic acids or derivatives thereof with formula (Ia) or (Ib) Condensation obtain,

Wherein D- is-OH ,-Cl or-OR', and wherein R' is C₁-C₄Alkyl group；R¹Selected from the group being made up of：

I) direct key,

A) formula-(CH₂)_zAlkylidene group, wherein z is 1 to 20, more preferably 1 to 10, even more preferably 2 to 6 simultaneously And even more preferably 4 integer, the alkylidene group most preferably replaced, wherein the substituted alkylidene group is by 1 or 2 A-OH groups, 1 or 2 methyl and/or methylene group, cycloalkylene group, sub- cycloalkenyl groups and/or arylene group Substitution, or

With the alkoxylated fats amine with formula (II),

Wherein R²Selected from the group being made up of：Alkyl with 8 to 24 carbon atoms, preferably 12 to 24 carbon atoms Group or formula

R⁴-O-(A′O)_wThe group of-T-, wherein；

R⁴Indicate the hydrocarbyl group with 8 to 24 carbon atoms, preferably 12 to 24 carbon atoms；

W is number in the range of 0 to 20, preferably 0 to 10 and more preferably 0 to 3；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；

T indicates there is 1 to 6 carbon atom；Preferably 1 to 4 carbon atom and the most preferably Asia of 2 to 3 carbon atoms Alkyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms, preferably 2 carbon atoms；

B indicates alkyl with 1 to 4 carbon atoms group or indicates benzyl group；

X is indicated in the range of 1 to 20, preferably in the range of 1 to 10, more preferably between 1 to 6 range Number；

S is 1,2 or 3, preferably 2 or 3；

Y is 0 or 1；

For prepare compound (1a), preferred alkoxylated fats amine has formula (IIa),

Wherein, AO, x and R²As defined above；

Or the contracting of the product of the partially or completely quaternized acquisition of the alkoxylated fats amine of formula (II) or (IIa) can be passed through It closes；Optionally according to the dicarboxylic acids of formula (I) it is reacted with according to described between formula (II) or the alkoxylated fats amine of (IIa) After carry out further reaction step, which part or whole nitrogen-atoms by with alkylating agent R³X react and it is quaternized, wherein R³It is hydrocarbyl group, preferably C₁-C₄Alkyl group or benzyl group, and X is to be derived from alkylating agent R³The anion of X.

It should be understood that when the compound of formula (II) or (IIa) contain more than one (AO)_xWhen group, the value of integer x can be each other It is independently same or different.Similarly, when there are more than one y, all " y " are identical or not independently of one another With.

It is ability that the esterification condensation occurred between formula (Ia) or formula (Ib) and the compound of formula (II) or formula (IIa), which reacts, Known to domain.Reaction preferably executes in the presence of esterification catalyst, the esterification catalyst such as Bronsted acidOr lewis acid (Lewis acid), such as methanesulfonic acid, p-methyl benzenesulfonic acid, hypophosphoric acid, citric acid or trifluoro Change boron (BF₃)。

When using dicarboxylic acid derivatives (wherein D is O-R ') of formula (Ia), the reaction is ester interchange, can be replaced Generation ground can execute in the presence of basic catalyst.Alternatively, other conventional skills well known by persons skilled in the art can be used Art, since other derivatives of dicarboxylic acids, such as since acid anhydrides or its acid chloride.

The reaction occurs in the case of being in or be not in the solvent with addition.If there is solvent during reaction, Then solvent reply is inert in esterification, such as toluene or dimethylbenzene.

Esterification condensation between compound (Ia) or (Ib) and (II) or (IIa) react suitably by optionally 5 to 2 to 20 hours periods of mixture are heated to realize at a temperature of between 120 DEG C with 280 DEG C under the decompression of 200mbar.

When the t in formula (1) is 0, product is tertiary polyesteramine compounds, and when t is 1, and product is polyester polyquaternary amine Compound.Quaternized is reaction type well known in the art.For quaternization process, alkylating agent R³X be suitably selected from by with The group of lower composition：Dimethyl suflfate, dithyl sulfate, dimethyl carbonate, benzyl chloride, methyl bromide, methyl chloride, methyl iodide, preferably Ground dimethyl suflfate or methyl chloride and its mixture.

It is quaternized compound (Ia) or (Ib) and the condensation product of (II) or (IIa) to be executed.It is also possible in the first step Implement in rapid according to the quaternized of formula (II) or the compound of (IIa), and then implements compound (Ia) or (Ib) and quaternary ammonium Change the esterification of compound (II) or (IIa).Part or all of nitrogen-atoms can by with alkylating agent such as methyl chloride or sulphur The reaction of dimethyl phthalate is esterified, to obtain the product being partially or completely esterified.In addition, both methods can be combined so that first The compound of partial quaternization is esterified and the polyester of gained is further quaternized.

Quaternization reaction usually executes in water or solvent such as isopropanol or ethyl alcohol or in its mixture.Other are substituted Property solvent can be ethylene glycol monobutyl ether, two (ethylene glycol) monobutyl ethers and other ethylene glycol and propylene glycol, such as monoethylene glycol and Diethylene glycol.The reaction temperature of quaternization reaction suitably 20 DEG C to 100 DEG C, preferably at least 40 DEG C, more preferably at least 50 DEG C and most preferably at least 55 DEG C and preferably no more than 90 DEG C in the range of.

Expression " completely quaternized " in the meaning of the present invention means " whole nitrogen-atoms are quaternized " or " product Whole nitrogen-atoms be quaternary ammonium ", it means that per g of compound basic nitrogen total amount be less than or equal to 0.2mmol, preferably Ground is less than or equal to 0.1mmol, more preferably less or equal to 0.05mmol.

Therefore, when the amount of basic nitrogen be less than or equal to 0.2mmol/g, preferably less or equal to 0.1mmol/g, more preferably It, such as can be for example by with 0.2N titration with hydrochloric acid or known in the art any other is suitable when ground is less than or equal to 0.05mmol/g Method measure, preferably stop heating.

According to a preferred embodiment, whole nitrogen-atoms of product are quaternary ammoniums.

In one embodiment, dicarboxylic acids or derivative (Ia) or (Ib) and alkoxylated fats amine (II) or (IIa) Between molar ratio be 2:1 to 1:2, preferably 1.5:1 to 1:1.5, more preferably 1.4:1 to 1:1.4.

The group being made up of preferably is selected from according to the compound of formula (Ia) and formula (Ib)：Oxalic acid, malonic acid, amber Acid, glutaric acid, glutaconate, adipic acid, muconic acid, pimelic acid, phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, Malic acid, maleic acid, fumaric acid, suberic acid, mesaconic acid, decanedioic acid, azelaic acid, tartaric acid, itaconic acid, glutinicacid, lemon health The methyl esters or ethyl ester of acid, brassylic acid, dodecanedioic acid, traumatic acid, thapsic acid, corresponding acid chloride, these compounds Or acid anhydrides and its mixture, the group being made up of more preferably is selected from according to the compound of formula (Ia) and formula (Ib)：Oxalic acid, It is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, tetrahydrophthalic acid, malic acid, tartaric acid, right The methyl esters or ethyl ester or acid anhydrides of the acid chloride, these compounds answered and its mixture, and most preferably adipic acid；

Preferably according to formula (II) or the compound of (IIa) by the alkoxylate of the amine selected from the group being made up of come It prepares：2 ethyl hexylamine, 2- propyl heptyl amice, n-octyl amine, n-Decylamine, n-dodecane amine, (Cocoalkyl)-amine, (palm oil alkane Base)-amine, n-tetradecane base amine, n-hexadecyl amine, n-octadecane base amine, oleyl amine, (tallow alkyl)-amine, (h-tallow alkane Base)-amine, (rapeseed alkyl)-amine, (soya alkyl)-amine, erucic amide, N- (positive decyl)-N- methyl-trimethylenes-diamines, N- (dodecyl)-N- methyl-trimethylenes-diamines, N- (Cocoalkyl)-N- methyl-trimethylenes-diamines, N- (rapes Seed alkyl)-N- methyl-trimethylenes-diamines, N- (soya alkyl)-N- methyl-trimethylenes-diamines, N- (tallow alkyl)- N- methyl-trimethylenes-diamines, N- (hydrogenated tallow alkyl)-N- methyl-trimethylenes-diamines, N- (erucic acid)-N- methyl-three Methylene-diamines, isotridecyl oxygen propylamine and its mixture, more preferably (Cocoalkyl)-amine or (tallow alkyl)- Amine.

In one embodiment, 2 to 20, preferably 2 to 10 ethoxy units of fatty amine as described above and/ Or 2 to 20, preferably 2 to 10 propoxy units and/or 2 to 20, preferably 1 to 10 butoxyl unit alkoxylates To obtain according to formula (II) or the compound of (IIa).The random alkoxylated polymerization product of formula (II) or (IIa) can be by using ethoxies The mixture of base unit, propoxy unit and butoxyl unit obtains.Block (Block) can be by continuously adding alkoxy list Member, such as ethoxy unit is added first, propoxy unit is then added, and then add butoxyl unit to generate.Alkane Oxygroupization can be by any suitable method known in the art, by using such as basic catalyst such as potassium hydroxide or acidity Catalyst executes.

Example according to formula (II) or the commercial product of (IIa) include Noramox SD20, Noramox SD15, Noramox S11、Noramox S5、Noramox S7、Noramox S2、Noramox SH2、Noramox O2、Noramox O5, Noramox C2, Noramox C5 and Noramox C15, are all provided by French CE CA.The commercial product of formula (II) its His example includes that can be obtained from Air products companiesE-17-5 andE-T-2。

Preferred alkylating agent R³X is selected from the group being made up of：Dimethyl suflfate, dithyl sulfate, dimethyl carbonate, Benzyl chloride, methyl bromide, methyl chloride, methyl iodide and its mixture, more preferably dimethyl suflfate or methyl chloride.X is preferably It is single charge or double charge anion.

In formula (1) and (1a), x is in the range of 1 to 20, preferably in the range of 1 to 10 and more preferably Number in the range of 1 to 6.

The average value of formula (1) and the p in (1a) are depended on according to formula (Ia) or the compound of (Ib) and (II) or (IIa) Molar ratio and depend on reaction condition.In one embodiment, p is in the range of 1 to 15, preferably 1 to 10 In range and the number more preferably in the range of 1 to 5.

The compound of an embodiment according to the present invention, formula (1) or (1a) can have various groups, and therefore may be used The mixture of different compounds including formula (1) or (1a).

In addition, molecule may be present in the product mixtures not being esterified completely, but it is according to the product of formula (1) and (1a) Key compound.

In one embodiment, formula (1) or the compound of (1a) characterize as follows：

R¹It indicates with 1 to 20, preferably 1 to 10 carbon atom, more preferably with 2 to 6 carbon atoms, even more The preferably alkylidene group with 4 carbon atoms；

AO is polyoxyalkylene group, preferably ethoxy group；

X is to be derived from alkylating agent R³The anion of X；Preferably chlorion or sulfate radical

P is number in the range of 1 to 15；And

T is 0 or 1, preferably 1.

According to another embodiment, the compound of formula (1) or (1a) possess at least one of following characteristics：

R¹Derived from dicarboxylic acids, dicarboxylic acid chloride, the diester of dicarboxylic acids, dicarboxylic acids acid anhydrides, preferably R¹Derivative is free The compound of free group consisting of：Oxalic acid, malonic acid, succinic acid, glutaric acid, glutaconate, adipic acid, muconic acid, heptan Diacid, phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, malic acid, maleic acid, fumaric acid, suberic acid, mesaconic acid, Decanedioic acid, azelaic acid, tartaric acid, itaconic acid, glutinicacid, citraconic acid, brassylic acid, dodecanedioic acid, traumatic acid, it is general Sour, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or acid anhydrides and its mixture, more preferably R¹It is derived from Compound selected from the group being made up of：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, O-phthalic Acid, tetrahydrophthalic acid, malic acid, tartaric acid, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or acid anhydrides And its mixture, and most preferably adipic acid；

R³Derived from the alkylating agent selected from the group being made up of：Dimethyl suflfate, dithyl sulfate, carbonic acid diformazan Ester, benzyl chloride, methyl bromide, methyl chloride, methyl iodide and its mixture, preferably dimethyl suflfate or methyl chloride.

The collecting agent of a preferred embodiment according to the present invention, step b) is adipic acid and ethoxylation cocounut oil alkane The polymer of base amine (also referred to as (Cocoalkyl)-amine) (5OE), it is completely quaternized with methyl chloride.This polymer is being tested CA1 is prepared as in part.The collecting agent of another preferred embodiment according to the present invention, step b) is adipic acid and ethoxy The polymer of base tallow alkylamine (also referred to as (tallow alkyl)-amine) (5OE), it is completely quaternized with methyl chloride.It is this poly- It closes object and is prepared as CA2 in experimental section.The collecting agent of another preferred embodiment according to the present invention, step b) is for oneself The polymer of diacid and ethoxylated tallow alkylamine (also referred to as (tallow alkyl)-amine) (11OE), with methyl chloride complete season Ammonium.(OE) be the ethylene oxide equivalent reacted with fat alkylamine quantity.

The step c) of the method for the present invention

The step c) of the method for the present invention refers to by the material and step containing white pigment and impurity of step a) B) the collecting agent mixes in aqueous environment to form aqueous suspension.

An embodiment according to the present invention, the material containing white pigment and impurity of at least one step a) can be The suspension for mixing with water in first step, and then being obtained can be mixed with the collecting agent of step b) to form aqueous suspension Liquid.

The collecting agent of step b) can be mixed with water in the first step, and the suspension then obtained can be at least one Kind step a's) mixes containing the material of white pigment and impurity to form aqueous suspension.

Another embodiment according to the present invention, the material containing white pigment and impurity of at least one step a) and The collecting agent of step b) can be mixed with water in one step to form aqueous suspension.

Preferably, it mixes and wet milk, blending tank, feed pump or flotation agitator can be used to implement, for by collecting agent It is mixed into aqueous suspension.

Mixing can that is, at 20 DEG C ± 2 DEG C, or be implemented at a temperature of other at room temperature.According to an embodiment, it mixes Closing can be at a temperature of 5 DEG C to 40 DEG C, preferably 10 DEG C to 30 DEG C and most preferably 15 DEG C to 25 DEG C, or in other temperature Lower implementation.Heat can be introduced by internal shear or by external source or combinations thereof.

The solid content for the aqueous suspension that method through the invention obtains can pass through method tune known to technical staff Section.In order to adjust the aqueous material containing white pigment and impurity suspension solid content, suspension can by filtering, Centrifugation or thermal release method are partially or even wholly dehydrated.Alternatively, it can add water to containing white pigment and impurity Material, until obtain needed for solid content until.It additionally or alternatively, can be by containing in vain with appropriate lower content The suspension of the material of color pigment and impurity is added to aqueous suspension, until the solid content needed for obtaining.

A preferred embodiment according to the present invention, the aqueous suspension obtained in step c) have as hereinafter Consolidating between the 5 weight % and 80 weight % of the measured total weight based on the solid in suspension described in embodiment part Body content, between the preferably 10 weight % of the total weight based on the solid in suspension and 70 weight %, more preferably 20 weights It measures between % and 60 weight % and the most preferably solid content between 25 weight % and 55 weight %.

The aqueous suspension obtained in the step c) can have 7 to 10, preferably 7.5 to 9.5 and more preferably 8.5 to 9.0 pH.

It can amount addition below one or more collecting agents of the invention in step c)：Minerals based on step a) 1 to 5 000ppm of the gross dry weight of material, preferably amount are the 20 to 2 of the gross dry weight of the mineral material based on step a) 000ppm, more preferably amount is 30 to 1 000ppm, and most preferably amount is 50 to 800ppm.

The amount of the collecting agent of the present invention can be adjusted by considering the specific surface area of impurity.According to an embodiment, exist It can amount addition below collecting agent of the invention in step c)：1 to 100mg/m²The described of step a) contain white pigment Material impurity, preferably amount be 5 to 50mg/m²Step a) the material containing white pigment impurity, and Most preferably 10 to 45mg/m²Step a) the material containing white pigment impurity.The specific surface area of impurity is such as Hereinafter measuring described in embodiment part.

In addition to the material a) containing white pigment and impurity and collecting agent b), one or more other additives can be deposited It is in aqueous suspension.Possible additive be such as pH adjusting agent, solvent (water, one or more organic solvents and its Mixture)；Inhibitor, such as starch, yaruru, tannin, dextrin and guar gum and polyelectrolyte, such as polyphosphate and Waterglass is often combined with inhibitor effect with dispersant effect.Other conventional additives have been known to flotation field Infusion (foaming agent), such as methyl isobutyl carbinol, triethoxybutane, pine tar, terpinol and polypropylene oxide and its alkane Base ether, wherein methyl isobutyl carbinol, triethoxybutane, pine tar, terpinol are preferred foaming agents.Pass through non-limiting reality The mode of example, preferred conventional additives are typically foaming agent, and wherein terpinol is most common.

In addition, its known one or more other conventional collecting agent and preferably one or more routines in flotation field In the aqueous suspension that cation-collecting agent can be formed in step c).Preferred common cationic collecting agent is free from sulphur atom Those of, and most preferably only contain carbon, nitrogen and hydrogen atom and optionally those of oxygen atom.However, when salinization is sour originally When body includes one or more sulphur atoms (such as sulfuric acid, sulfonic acid or alkyl sulfonic acid), in the routine of itself and the addition salt form of acid Cation-collecting agent can contain one or more sulphur atoms.

It may be present in and may include but be not limited to from the example of the common cationic collecting agent in the suspension that step c) is obtained Fatty amine and its salt and its alkoxy derivative, fatty poly- (alkylene amines) and its salt, such as poly- (ethylene amines), poly- (propylidene amine) and its salt and its alkoxy derivative, fatty acid amide polyamine and its salt and its alkoxylate derive Object, fatty acid amide poly- (alkylene amines) and its salt and its alkoxy derivative, fatty imidazolines and its salt and its alkane Oxygroup derivative, N- fatty alkyls amino carboxylic acid and its salt, for example, N- fatty alkyls alanine and its salt, alkyl ether amine and Alkyl ether diamine and its salt, quaternary ammonium compound, such as fatty quaternary ammonium compound, single (fatty alkyl) quaternary ammonium compound, two (fat Alkyl) quaternary ammonium compound, those of described in 2007/122148 A1 of WO etc..

" polyamine " in the meaning of the present invention is the compound for including two or more amine groups, and amine groups may quilt Substitution, i.e., described two or more amine groups can be same or different and can be primary amine, secondary amine or tertiary amine groups Group.

It may be present in and may include from the particular instance of the common cationic collecting agent in the suspension that step c) is obtained but not It is limited to two cocounut oil-alkyl dimethyl ammonium chloride (CAS RN 61789-77-3), cocounut oil-dimethyl benzyl ammonium chloride (CAS RN 61789-71-7), tallow dimethyl benzyl ammonium chloride (CAS RN 61789-75-1), ethoxylated tallow monoamine, 1,3- third Two amine-n-butter diacetate esters (CAS RN 68911-78-4), N, N', N'- tri--ethoxy N- butter propane diamine (CAS RN61790-85-0), N, N', N'- tri--ethoxy N- oil bases propane diamine (CAS RN 103625-43-0), N, N', tri--hydroxyls of N'- Ethyl n-lauryl propane diamine (CAS RN 25725-44-4) is obtained by the condensation of diethylenetriamines and fatty acid oil Fatty alkyl imidazoline (CAS RN162774-14-3), N, N', tri--ethoxys of N'- N- docosyls-propane diamine (CAS RN91001-82-0), isodecyl oxygroup propyl -1,3- diaminopropanes (CAS RN 72162-46-0), N, (the butter carboxylics of N- bis- Ethyl)-N- ethoxy-N- methylammonium-methosulfates (CAS RN91995-81-2), N- cocounut oil-Beta-alanine (CAS RN 84812-94-2), N- lauryls-Beta-alanine (CAS RN 1462-54-0), N- myristyls-Beta-alanine (CAS RN14960-08-8), the addition salts, the sodium salt (CAS RN3546-96-1) of N- lauryls-Beta-alanine, the N- months of itself and acid The triethanolamine salt (CAS RN14171-00-7) of Gui Ji-Beta-alanine, the triethanolamine of N- myristyls-Beta-alanine The mixture of two or more etc. in salt (CAS RN61791-98-8) and the above compound of all proportions.

" ether amines " and " ether diamine " in the meaning of the present invention are comprising at least one ether and difference NH₂End group and NH₂ The compound of end group and another primary amine, secondary amine or tertiary amine group.

If there are additive and/or conventional collecting agent in suspension, the collecting agent of the present invention can be relative to collecting The 1 weight % to 100 weight % of the total amount of agent and other additive, more preferably 10 weight %100 weight %, usual 20 weight % to 100 weight % and advantageously 1 weight % to 99 weight %, more preferably 10 weight % are measured to 99 weight %, usual 20 Weight % to 99 weight % exists.

The step d) of the method for the present invention

The step d) of the method for the present invention refers to the suspension by being formed in step c) by gas.

Gas can be by being introduced into positioned at one or more of the lower half of container entrance in the container of step d).It is alternative Ground or in addition, gas can be introduced by the entrance on the agitating device in the container.Then gas travels naturally through outstanding Supernatant liquid is raised above.

Preferably, the gas in the present invention can be air.

Air Bubble Size of the gas in suspension can between 0.01 and 10mm, preferably between 0.05 and 5mm and Most preferably between 0.1 and 2mm.

Gas flow rate in step d) can be in 4dm³It is adjusted in flotation cell, such as in 0.1 and 30dm³Between/min, preferably In 1 and 10dm³Between/min and more preferably in 3 and 7dm³Between/min.

Agitator bath and/or flotation column and/or gas may be used in a preferred embodiment according to the present invention, step d) Dynamic flotation unit and/or the flotation unit characterized by gas injection.

A preferred embodiment according to the present invention, the aqueous suspension in step d) can have in 5 DEG C and 90 DEG C Between, preferably between 10 DEG C and 70 DEG C, more preferably between 20 DEG C and 50 DEG C and most preferably in 25 DEG C and 40 DEG C Between temperature.

Step d) is preferably executed under agitation.In addition, step d) can be continuous or discontinuous.

According to a preferred embodiment, step d) is executed, until not re-forming foams or can not visually observe again Until foams or until can not be regathered until impurity in foams.

The step e) of the method for the present invention

The step e) of the method for the present invention refers to by being taken out with white in the aqueous suspension of acquisition after step d) Pigment mutually recycles the product containing white pigment.

The method of the present invention includes at least one indirect flotation steps.Compared to conventional flotation, wherein desirable white Color pigment is directly floated and is collected from the foam of generation, and reverse flotation or indirect flotation are intended to keep undesirable impurity preferential Ground is floated and is removed, to leave the suspension being concentrated in desirable white pigment.It is of the invention according to the present invention Method results in the foam containing impurity and the phase with white pigment with the product containing white pigment.Hydrophobization is miscellaneous During matter moves to the surface of suspension and the supernatant foams or foam that are concentrated at surface.This foams can be by using Such as it is skimmed from surface or is held simply by making foams overflow and be passed to individually to collect by foams by scraper It is collected in device.After collecting foams, mutually will with white pigment containing the product with non-floating white pigment It stays.The product containing white pigment stayed in aqueous suspension can by filter with remove aqueous phase, by decantation or It is collected by the other modes commonly employed in the art for detaching liquid with solid.

The collected product containing white pigment can be subjected to according to the present invention or froth flotation side according to prior art One or more other froth flotation steps of method.

According to a preferred embodiment, the phase with white pigment obtained from step e) can be before step e) And/or it mills later.

Step of milling can be implemented with any conventional milling device, such as by using ball mill, hammer-mill, rod milling Machine, oscillating mill, kibbler roll, centrifugation impact grinder, vertical type pearl-grinding machine, grater, needle mill, hammer-mill.So And any other device for the product containing white pigment recycled during method and step e) that can mill can be used.

The present invention method step e) after can carry out for example by wet-milling and screening carry out it is at least one mill or Classification step is to obtain fine grinding product slurry, and/or carries out at least one other processing step.

The hydrophobization impurity of method acquisition through the invention and the hydrophobization silicate being preferably contained in foams can It is collected as described above.In a preferred embodiment in accordance with this invention, hydrophobization impurity may include the silicon with white Hydrochlorate, such as such as wollastonite, kaolin, kaolinite clay, the kaolinite clay of calcining, montmorillonite, talcum, diatomite or Hai Pao Stone.It is highly preferred that hydrophobization impurity by with white silicate form, and it is highly preferred that impurity only by it is a kind of white The silicate of color forms.For example, impurity can only by wollastonite or kaolin or kaolinite clay or calcining kaolinite clay or Montmorillonite or talcum or diatomite or sepiolite composition.Method for floating acquisition according to the present invention and this detached with white pigment A little impurity can be further processed and in suitably application.When only containing by solar radiation of method acquisition through the invention Silicate with white appearance and preferably only contain by a kind of white silicate with white appearance when solar radiation Impurity can mode identical with the product containing white pigment be used for such as paper, plastics, paint, coating, concrete, water In mud, cosmetics, water process, food, pharmacy, ink and/or agricultural application.

The product containing white pigment that method through the invention obtains

In a preferred embodiment, the product containing white pigment that method through the invention obtains may include At least white pigment of 95 weight % based on dry weight, preferably at least 98 weight %, more preferably at least 99 based on dry weight The white pigment of weight % and most preferably at least 99.9 weight %.

In another embodiment, the product containing white pigment that method through the invention obtains may include being based on Dry weight is less than 60ppm, preferably less than 35ppm, the even more preferably less than collecting agent of 15ppm and more preferably less than 5ppm Or its catabolite.

The product containing white pigment and mutually can be used for paper with white pigment that method through the invention obtains It opens, in plastics, paint, coating, concrete, cement, cosmetics, water process, food, pharmacy, ink and/or agricultural application.It is preferred that Ground, the product containing white pigment can be used in wet-end process, cigarette paper, cardboard and/or the coating application of paper machine, or be used as Rotogravure printing and/or offset printing and/or ink jet printing and/or continuous ink jet printing and/or aniline printing and/or electrofax And/or ostentatious support.

In the case where term " includes (comprising) " use in the specification and claims of the present invention, it is not Exclude other elements.For purposes of the present invention, term " Consists of " is considered as term " including (comprising of) " Preferred embodiment.If hereinafter group is defined as to include at least a certain number of embodiments, it will also be understood that For the open group being preferably only made of these embodiments.

Using indefinite article or definite article when referring to singular noun, for example, " one/a kind of (a) ", " one/a kind of (an) ", in the case of " (the) ", this includes the plural form of the noun, unless stated otherwise other situation.

Term is used interchangeably as " obtainable " or " definable " and " acquisition " or " definition ".This means that For example, unless in addition context is clearly specified, otherwise term " acquisition ", which is not intended to instruction such as embodiment, to pass through Such as term " acquisition " sequence of steps is followed to obtain, although this limited understanding always by term " acquisition " or " is determined Justice " include for preferred embodiment.

Based on the certain embodiments for being intended to illustrate invention and it is non-limiting following embodiment, it will be more preferable geographical Solve the scope of the present invention and purpose.

In view of the above, some aspects of the invention are related to：

1. the method for manufacturing the product containing white pigment, it is characterised in that the described method comprises the following steps：

A) at least one material containing white pigment and impurity is provided；

R⁴Indicate the hydrocarbyl group with 8 to 24 carbon atoms；

W is number in the range of 0 to 20；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 6 carbon atom；

R³Selected from the group being made of hydrocarbyl group or benzyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms；

X indicates to be derived from alkylating agent R³The anion of X；

X is number in the range of 1 to 20；

P is number in the range of 1 to 15；

T is 0 or 1；

Y is 0 or 1；And

The group of G expressions (2)；

Wherein；

B indicate alkyl with 1 to 4 carbon atoms group or

Indicate benzyl group；

S is 1,2 or 3；

R³, X and t it is as defined above；

N⁺The R being connected in formula (1)²；And

(CH₂)_sThe quaternary nitrogen atoms being connected in formula (1)；

D) gas is passed through into the suspension of the formation in step c)；

2. according to the method for aspect 1, wherein the method is related to indirect flotation step, results in containing impurity Foam and the phase with white pigment with the product containing white pigment.

3. the method according to any one of in terms of foregoing, wherein the white pigment is white mineral matter pigment, it is excellent Selection of land is selected from the group being made up of：Natural whiting or powdered whiting, packet mineral material calciferous, dolomite, The mixture of barite, aluminium oxide, titanium dioxide and aforementioned substances.

4. the method according to any one of in terms of foregoing, wherein the white mineral matter pigment is alkaline-earth metal carbonic acid Salt, preferably calcium carbonate and most preferably powdered whiting.

5. the method according to any one of in terms of foregoing, wherein the material containing white pigment include selected from by The impurity of group consisting of：Iron sulfide, iron oxide, graphite, silicate and its mixture.

6. according to the method described in aspect 5, wherein the silicate is selected from the group being made up of：Quartz, mica, angle are dodged Rock, feldspar, clay mineral and its mixture, and preferably quartz.

7. according to the method described in aspect 5, wherein the silicate is the color white selected from the group being made up of Silicate：Wollastonite, kaolin, kaolinite clay, the kaolinite clay of calcining, montmorillonite, talcum, diatomite, sepiolite with And its mixture.

8. the method according to any one of in terms of foregoing, the material containing white pigment and impurity of wherein step a) In the amount of white pigment be the 0.1 weight % based on dry weight to 99.9 weight %, the preferably 30 weight % based on dry weight are extremely 99.7 weight %, more preferably 60 weight % are to 99.3 weight %, and most preferably 80 weight % to 99 weight %.

9. the method according to any one of in terms of foregoing, the material containing white pigment and impurity of wherein step a) Middle white pigment:The ratio of impurity is 0.1 based on dry weight:99.9 to 99.9:0.1, preferably 30 based on dry weight:70 to 99.7:0.3, more preferably 60:40 to 99.3:0.7, and most preferably 80:20 to 99:1.

10. the method according to any one of in terms of foregoing, the material containing white pigment and impurity of wherein step a) The weight median particle of material at 1 to 1 000 μm, preferably 3 to 700 μm, more preferably 5 to 500 μm and most preferably 10 to In the range of 80 μm or 100 to 400 μm.

11. the method according to any one of in terms of foregoing, wherein the compound of the formula (1) characterizes as follows：

R²Indicate hydrocarbyl group or formula R containing 12 to 24 carbon atoms⁴-O-(A′O)_wThe group of-T-；Wherein

R⁴Indicate the hydrocarbyl group with 12 to 24 carbon atoms；

W is number in the range of 0 to 10, preferably 0 to 3；

A ' O indicate the polyoxyalkylene group with 2 to 4 carbon atoms；And

R³Indicate alkyl with 1 to 4 carbon atoms group；

X indicates halogen, sulfate radical or carbonate；

P is number in the range of 1 to 10, preferably in the range of 1 to 5.

12. the method according to any one of in terms of foregoing, wherein the compound such as provided in step b) be selected from by The group of the compound composition of formula (1a)：

Wherein,

AO、p、t、x R¹、R²、R³With X as defined in claim 1, preferably as defined in terms of 11.

13. according to the method described in aspect 12, wherein the compound of the formula (1a) characterizes as follows：

R¹It indicates with 1 to 10 carbon atom, preferably with 2 to 6 carbon atoms and more preferably with 4 carbon originals The alkylidene group of son；

AO is polyoxyalkylene group, preferably ethoxy group；

P is number in the range of 1 to 15；And

T is 0 or 1, preferably 1.

14. according to the method for aspect 12 or 13, wherein the compound of the formula (1a) possesses at least one in following characteristics It is a：

R¹Derived from dicarboxylic acids, dicarboxylic acid chloride, the diester of dicarboxylic acids, dicarboxylic acids acid anhydrides, preferably R¹Derivative is free The compound of free group consisting of：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, Tetrahydrophthalic acid, malic acid, tartaric acid, itaconic acid, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or Acid anhydrides and its mixture, preferably adipic acid；

R²Derived from the fatty amine selected from the group being made up of：2 ethyl hexylamine, 2- propyl heptyl amice, n-octyl amine, the positive last of the ten Heavenly stems Amine, n-dodecane amine, (Cocoalkyl)-amine, (palm alkyl) amine, n-tetradecane base amine, n-hexadecyl amine, n-octadecane base Amine, oleyl amine, (tallow alkyl)-amine, (hydrogenated tallow alkyl)-amine, (rapeseed alkyl)-amine, (soya alkyl)-amine, erucic amide, N- (positive decyl)-N- methyl-trimethylenes-diamines, N- (dodecyl)-N- methyl-trimethylenes-diamines, N- (cocounut oil alkane Base)-N- methyl-trimethylenes-diamines, N- (rapeseed alkyl)-N- methyl-trimethylenes-diamines, N- (soya alkyl)-N- Methyl-trimethylene-diamines, N- (tallow alkyl)-N- methyl-trimethylenes-diamines, N- (hydrogenated tallow alkyl)-N- methyl- Trimethylene-diamines, N- (erucic acid)-N- methyl-trimethylenes-diamines, isotridecyl oxygen propylamine and its mixture, preferably Ground (Cocoalkyl)-amine or (tallow alkyl)-amine；

15. the method according to any one of in terms of foregoing, the wherein collecting agent of step b) are by one or more formulas (1) Or the compound composition of (1a).

16. the method according to any one of in terms of foregoing, wherein the aqueous suspension obtained in step c) has 7 To 10, preferably 7.5 to 9.5 and more preferably 8.5 to 9.0 pH.

17. the method according to any one of in terms of foregoing, wherein to be caught described in amount below addition in step c) Receive agent：1 to 5 000ppm of the gross dry weight of the material containing white pigment and impurity based on step a), preferably amount is to be based on 20 to 2 000ppm of the gross dry weight of the material containing white pigment and impurity of step a), more preferably amount is 30 to 1 000ppm, and most preferably amount is 50 to 800ppm.

18. the method according to any one of in terms of foregoing, wherein the aqueous suspension obtained in step c) has Solid content between the 5 weight % and 80 weight % of total weight based on the solid in suspension, based on consolidating in suspension Between the preferably 10 weight % of the total weight of body and 70 weight %, between more preferably 20 weight % and 60 weight % and most Solid content between preferably 25 weight % and 55 weight %.

19. the method according to any one of in terms of foregoing, wherein before, during or after step c) by a kind of or Multiple additives are added to aqueous suspension, and wherein additive is selected from the group being made up of：PH adjusting agent, solvent, inhibitor, Polyelectrolyte, foaming agent and the collecting agent other than according to the collecting agent of formula (1) and/or (1a).

20. the method according to any one of in terms of foregoing, wherein the aqueous suspension obtained in step c) is in step It is rapid c) during and/or after mill.

21. the method according to any one of in terms of foregoing, the gas in wherein step d) is air.

22. the method according to any one of in terms of foregoing, the wherein suspension in step have 5 DEG C with 40 DEG C it Between, preferably between 10 DEG C and 40 DEG C, more preferably between 10 DEG C and 30 DEG C and most preferably 15 DEG C with 25 DEG C it Between temperature.

23. the method according to any one of in terms of foregoing, wherein the phase with white pigment obtained from step e) Disperseed and/or milled before or after step e), and preferably at least one dispersant and/or at least one It kind mills and to be disperseed in the presence of auxiliary agent and/or be milled.

24. can by the method according to any one of in terms of foregoing obtain the phase with white pigment in the following Purposes：Paper, plastics, paint, coating, concrete, cement, cosmetics, water process, food, pharmacy, ink and/or agricultural are answered With wherein the product containing white pigment is preferably used for wet-end process, cigarette paper, cardboard and/or the coating application of paper machine In, or as rotogravure printing and/or offset printing and/or ink jet printing and/or continuous ink jet printing and/or aniline printing and/ Or electrofax and/or ostentatious support.

Embodiment

1 measurement method

PH is measured

Mettler Toledo Seven Easy pH meters and Mettler Toledo are used at 25 DEG C Expert Pro pH electrode measurements pH.The commercially available buffering with 4,7 and 10 pH value being firstly used at 20 DEG C Solution (coming from Aldrich) measures 3 points of calibrations (according to segmentation method) of value.The pH value of report is to pass through instrument The end point values of detection (when terminal is that deviation average is less than 0.1mV in past 6 seconds when the signal of measurement).

Size distribution (the diameter of granular materials<The granular mass % of X) and weight median particle (d₅₀)

Size distribution (PSD) and relevant median particle diameter d₅₀It is measured by sub-laser diffraction analyzer；In d₅₀Higher than 5 μ Measured by Malvern Mastersizer 2000 in the case of m or finer material (<5 μm) in the case of Pass through Micromeritics Sedigraph^TM5120 measure.In the Na4P of 0.1 weight %₂O₇Aqueous solution in it is real Testing amount, and be ultrasonically treated sample dispersion and later using high speed agitator.Although sedigraph (Sedigraph) It is played a role by sedimentation method (analysis of the settling behavior i.e. in gravitational field), but Mastersizer is with circulation pattern Operation.

The solid weight (weight %) of material in suspension

By the way that the total weight of the weight of solid material divided by aqueous suspension is determined solid weight.Passed through by weighing It evaporates the aqueous phase of suspension and dries the material obtained and determine solid to constant weight and the solid material that obtains The weight of material.

Specific surface (BET) measures

Using nitrogen and BET methods, (it is (ISO 9277 known to technical staff:2010) white pigment or miscellaneous) is determined The specific surface area of matter is (with m²/ g is counted).Then by specific surface area is multiplied with the quality of white pigment or impurity (in terms of g) come The total surface area of white pigment or impurity is obtained (with m²Meter).The method and instrument be known to technical staff, and usually Specific surface for determining white pigment and impurity.

Brightness measurement and yellow colour index (=YI)

Sample from method for floating is dried by using microwave.Obtained dried powder is prepared in powder press To obtain flat surfaces, and the ELREPHO 3000 from Datacolor companies is used, Tappi is measured according to ISO 2469 Brightness (R457ISO brightness).The result of Tappi brightness is provided as the percentage compared with calibration standard.

Yellow colour index is calculated by the following formula：

YI=100* (R_x-R_z)/R_y)

The determination of HCl insolubles contents

10g roughages (dry products or slurry that consider solid content) are weighed in 400ml beakers, 50ml is suspended in It goes to mix in minerals (demin.) water and with 40ml HCl (8N=25%).After the formation of carbon dioxide is completed, it will mix It closes object to boil 5 minutes, is cooled to room temperature and is then filtered dry on the molecular filter previously weighed.Beaker is removed into minerals with 20ml Water rinses 3 times, and later that filter is dry in microwave at 105 DEG C, until reaching constant weight.In filter dry It in dry device after cooling, weighs again to it, and HCl insoluble matters (insol.) content is calculated according to following formula：

The determination of load capacity

The titration carried out using sodium apolate (Na-PES), by M ü tek particle charge detectors (from BTG's PCD04) surface charge of the particle with collecting agent in the slurry in terms of [μ Val/Kg] is determined.

The determination of acid value

It as reagent and uses isopropanol as solvent using potassium hydroxide solution, acid value is measured by constant-current titration.

In 250mL beakers, it is precisely weighed the sample to be analyzed of (Sw is accurate to mg) about 10g, and adds 70mL's Isopropanol.If desired, being gently agitated for and heating mixture to obtain homogeneous samples.The glass reference electrode of titrator will be combined It is introduced into solution, then the solution is stirred with magnetic stirrer.Sample is executed using 0.1N potassium hydroxide (KOH) aqueous solution Acid base titration, and pH variations are recorded on titrator.It is determined to graphically using method known to those skilled in the art Stoichiometric point, and determine the volume (V of the potassium hydroxide solution for reaching this point_KOH, in terms of mL).Then according to following meter It calculates and obtains acid value (AV)：

2 collecting agents

The synthesis of collecting agent 1 (CA1)

By the cocoalkyl amines of 2025.8g ethoxylations, (Noramox C5 are provided by French CE CA, include 5 moles of second Oxygroup group) and 0.2g hypophosphorous acid (50%) be introduced into 4 liters of round-bottomed flasks.It is heated the mixture in the case where nitrogen is bubbled 80 DEG C, stops being bubbled later and add 503.7g adipic acids under agitation.After 15 min, by the temperature of mixture 1 It is increased to 160 DEG C in hour and continuously decreases the pressure in container, until the pressure for reaching 6.67kPa (50mm Hg) is Only.It after 1 hour, heats the mixture to 200 DEG C under 160 DEG C and 6.67kPa and mixture is kept 4 at this temperature Hour.Later, 220 DEG C are raised the temperature to and is maintained, until nearly all acid is consumed (acid value<Until 5meq/g).It will mix It closes object and is cooled to 60 DEG C, and the ester amine of gained (3) is recycled and is further processed without any.

2000g ester amines (3) are added in 6 liters of glass reactors, and add 300g isopropanols.Methyl chloride is added, until Until pressure in glass reactor reaches 2.9 bars, then raises the temperature to 85 DEG C and hold the mixture in 80 DEG C extremely Between 85 DEG C, until reaction completely occurs (when the total amount of basic nitrogen is less than or equal to 0.2mmol g^-1(such as by in isopropanol 0.2N titration with hydrochloric acid measure) when, realize completely reaction) until.Mixture is set to be cooled to 65 DEG C and be down to pressure later Atmospheric pressure.After being bubbled nitrogen by mixture 2 hours, the collecting agent 1 (CA1) obtained is recycled and uses isopropanol To reach the isopropanol content of 30 weight %, such as determined by gas chromatographic analysis appropriate.Collecting agent (CA1) is also referred to as oneself two The polymer of acid and ethoxylated cocoalkyl amine (also referred to as (Cocoalkyl)-amine) (5OE), with the complete quaternary ammonium of methyl chloride Change.

The synthesis of collecting agent 2 (CA2)

By the tallow alkylamine of 2201.7g ethoxylations, (Noramox S5 are provided by French CE CA, include 5 moles of second Oxygroup group) and 0.2g hypophosphorous acid (50%) be introduced into 4 liters of round-bottomed flasks.It is heated the mixture in the case where nitrogen is bubbled 80 DEG C, stops being bubbled later and add 503.7g adipic acids under agitation.After 15 min, by the temperature of mixture 1 It is increased to 160 DEG C in hour and continuously decreases the pressure in container, until the pressure for reaching 6.67kPa (50mm Hg) is Only.It after 1 hour, heats the mixture to 200 DEG C under 160 DEG C and 6.67kPa and mixture is kept 4 at this temperature Hour.Later, 220 DEG C are raised the temperature to and is maintained, until nearly all acid is consumed (acid value<Until 5meq/g).It will mix It closes object and is cooled to 60 DEG C, and the ester amine of gained (4) is recycled and is further processed without any.

2 038.9g ester amines (4) are added in 6 liters of glass reactors, and add 305.8g isopropanols.Methyl chloride is added, Until the pressure in glass reactor reaches 2.9 bars, then raises the temperature to 85 DEG C and hold the mixture in 80 DEG C between 85 DEG C, until reaction completely occurs (when the total amount of basic nitrogen is less than or equal to 0.2mmol g^-1(such as by with isopropyl 0.2N titration with hydrochloric acid in alcohol measures) when, realize reaction completely) until.Mixture is set to be cooled to 65 DEG C and by pressure later It is down to atmospheric pressure.After being bubbled nitrogen by mixture 2 hours, the collecting agent 2 (CA2) obtained is recycled and uses isopropanol Dilution is such as determined by gas chromatographic analysis appropriate with reaching the isopropanol content of 30 weight %.Collecting agent (CA2) is also referred to as The polymer of adipic acid and ethoxylated tallow alkylamine (also referred to as (tallow alkyl)-amine) (5OE), with methyl chloride complete season Ammonium.

Collecting agent 3 (CA3) (comparative)

18 AS of reagent Lupromin FP,Polymer esters quaternary ammonium salt, can be commercially available from BASF.

Collecting agent 4 to 15 (CA4 to CA15)

Other collecting agents (CA4 to CA15) are followed as prepared by same reaction conditions in embodiment 1 and pass through below Following compound reaction is set to obtain：

Table 1：Collecting agent CA4 to CA15.

In table 1, pass through the alkoxylated fatty amine for playing Source Description formula (II) of aliphatic alkyl chain.With fat alkylamine The quantity of ethylene oxide (OE) equivalent of reaction provides in bracket.Whole collecting agent CA4 to CA15 are completely quaternized.

Collecting agent CA4 to CA15 is also shown in the method according to the present invention for manufacturing the product containing white pigment Go out good characteristic.

3 float tests

Whole float tests are under room temperature (20 DEG C ± 2 DEG C) in the Outotec experiments equipped with conical inflatable agitator In the flotation cell of room, under the agitation of 1 600rpm, 4dm is used³Volumetric glass slot executes.It is added to the aqueous of flotation device to contain The solid content of the material suspension of white pigment and impurity is by dry weight 33%, described containing white pigment and impurity Material source is in the deposition marble rock deposit with Different Origin for having run method for floating.Water used is from each The precursor tap water of local method for floating.

The typical of 80% flotation agent is provided in on-test and implements dosage, and is mixed in regulating time at 2 minutes.Root According to the foam product realized and in slot, visible impurity adds the second dosage.

Then by the flotation gas being made of air by the hole of the axis location along agitator in about 2dm³/ min's It is introduced under rate.

The foams generated at the surface of suspension are detached from suspension by overflowing and skimming, until can not be again Until being collected into foams, and both remaining suspension and the foams of collection are dehydrated and dried and is used for matter to be formed Two kinds of concentrates that amount balance and quality analysis are determined as carbon fraction.

Comparing embodiment indicates " C " after embodiment number.

Embodiment 1 to 3

For embodiment 1 to 3, select the Gummern marble deposits from Austria contains white pigment and miscellaneous The material of matter.The material, which contains, to be determined by carbon fraction come the impurity of the 3.21 weight % determined.Material is crushed and is ground in advance 20 μm of intermediate value is milled to mill size d₅₀.The material is handled according to the above method.Test data is summarized in the following table 2.

Table 2：Float test.

A) impurity is expressed as insoluble in the compound in 8N HCl.

Such as can be collected from embodiment 1 to 6, the method for manufacturing the product comprising white pigment of the invention is shown Go out good result (a small amount of impurity in the product containing white pigment, the high level of Tappi brightness and yellow colour index it is low Value), or even a small amount of collecting agent (test No. 2 or 3 in aqueous suspension：It is also such under 400ppm).According to comparing The method of embodiment 7C to 9C is using collecting agent according to prior art and generates the product for including larger amount of impurity.With phase Comparison (2,5 and 7C of the test No.) display of the product of the collecting agent purifying of same amount by using obtaining according to the method for the present invention Product have less amount of impurity.

4 stability tests

For the stability of investigational agent, it is concurrently stirred for 24 hours at 20 DEG C and at 40 DEG C, and by using The time that Na-PES limits the reduction control of positive Mytek charges as anionic titrant.The product of gained is used for later The laboratory flotation test being compared with primary product.Flotation test carries out under 8.5 to 9 neutral pH.

In table 3：Stability test.

The load capacity of collecting agent according to the present invention reduces 21% and at 40 DEG C after about for 24 hours at 20 DEG C 28% is reduced, and collecting agent shows that 49% load capacity is reduced and shown at 40 DEG C at 20 DEG C according to prior art 58% load capacity is reduced.The result confirms that collecting agent according to the present invention is shown compared with prior art collecting agent more High stability.

It is used in combination with original collecting agent (test No. 10 and 12C) according to the float test of the condition such as provided in part 3 Implementing as the collecting agent (test No. 11 and 13C) of 1 weight % aqueous solutions for 24 hours is stored at 40 DEG C.

Table 4：Float test.

A) impurity is expressed as insoluble in the compound in 8N HCl.

Confirm that the performance of collecting agent according to the present invention after storage and before is higher than with result shown in upper table 4 The performance of prior art collecting agent.Even if after storage for 24 hours, the performance of collecting agent according to the present invention is existing also above original The performance (comparison of test No. 11 and test No. 12C) of technology collecting agent.

Claims

A) at least one material containing white pigment and impurity is provided；

R¹Selected from the group being made up of：

I) direct key,

ii)C₁-C₂₀The saturation or aliphatic unsaturated hydrocarbon of linear chain or branched chain, the hydrocarbon chain is optionally by one or more-OH groups, one A or multiple methyl and/or methylene group, cycloalkylene group, sub- cycloalkenyl groups and/or arylene group substitution, preferably Ground is

A) the alkylidene group with 1 to 20, more preferably 1 to 10 carbon atom, the alkylidene group most preferably replaced, The wherein described substituted alkylidene group is by 1 or 2-OH group, 1 or 2 methyl and/or methylene group, cycloalkylidene base Group, sub- cycloalkenyl groups and/or arylene group substitution, or

B) the alkenylene group with 1 to 20, preferably 1 to 10 carbon atom, the alkenylene group more preferably replaced, Described in the alkenylene group that replaces by 1 or 2-OH group, 1 or 2 methyl and/or methylene group, cycloalkylene group, Sub- cycloalkenyl groups and/or arylene group substitution；

R²Selected from by hydrocarbyl group or formula R with 8 to 24 carbon atoms⁴-O-(A′O)_wThe group of the group composition of-T-, wherein；

R⁴Indicate the hydrocarbyl group with 8 to 24 carbon atoms；

W is number in the range of 0 to 20；

A ' O are the polyoxyalkylene groups with 2 to 4 carbon atoms；And

T indicates the alkylidene group with 1 to 6 carbon atom；

R³Selected from the group being made of hydrocarbyl group or benzyl group；

AO indicates the polyoxyalkylene group with 2 to 4 carbon atoms；

X indicates to be derived from alkylating agent R³The anion of X；

X is number in the range of 1 to 20；

P is number in the range of 1 to 15；

T is 0 or 1；

Y is 0 or 1；And

The group of G expressions (2)；

Wherein；

B indicate alkyl with 1 to 4 carbon atoms group or

Indicate benzyl group；

S is 1,2 or 3；

R³, X and t it is as defined above；

N⁺The R being connected in formula (1)²；And

(CH₂)_sThe quaternary nitrogen atoms being connected in formula (1)；

C) by the collecting agent of the material containing white pigment and impurity of step a) and step b) in aqueous environment Mixing is to form aqueous suspension；

D) gas is passed through into the suspension of the formation in step c)；

2. according to the method described in claim 1, wherein the method is related to indirect flotation step, result in containing described miscellaneous The foam of matter and the phase with white pigment with the product containing white pigment.

3. excellent according to any method of the preceding claims, wherein the white pigment is white mineral matter pigment Selection of land is selected from the group being made up of：Natural whiting or powdered whiting, packet mineral material calciferous, dolomite, The mixture of barite, aluminium oxide, titanium dioxide and aforementioned substances.

4. according to any method of the preceding claims, wherein the white mineral matter pigment is alkaline-earth metal carbonic acid Salt, preferably calcium carbonate and most preferably powdered whiting.

5. according to any method of the preceding claims, wherein the material containing white pigment include selected from by The impurity of group consisting of：Iron sulfide, iron oxide, graphite, silicate and its mixture.

6. according to the method described in claim 5, the wherein described silicate is selected from the group being made up of：Quartz, mica, angle are dodged Rock, feldspar, clay mineral and its mixture, and preferably quartz.

7. according to the method described in claim 5, the wherein described silicate is the color white selected from the group being made up of Silicate：Wollastonite, kaolin, kaolinite clay, the kaolinite clay of calcining, montmorillonite, talcum, diatomite, sepiolite with And its mixture.

8. according to any method of the preceding claims, wherein step a's) is described containing white pigment and impurity The amount of white pigment in material is the 0.1 weight % based on dry weight to 99.9 weight %, preferably 30 weights based on dry weight % to 99.7 weight % is measured, more preferably 60 weight % are to 99.3 weight %, and most preferably 80 weight % to 99 weight %.

9. according to any method of the preceding claims, wherein step a's) is described containing white pigment and impurity White pigment in material:The ratio of impurity is 0.1 based on dry weight:99.9 to 99.9:0.1, preferably 30 based on dry weight:70 To 99.7:0.3, more preferably 60:40 to 99.3:0.7, and most preferably 80:20 to 99:1.

10. according to any method of the preceding claims, wherein the described of step a) contains white pigment and impurity Material weight median particle at 1 to 1 000 μm, preferably 3 to 700 μm, more preferably 5 to 500 μm and most preferably In the range of 10 to 80 μm or 100 to 400 μm.

11. according to any method of the preceding claims, wherein the compound of the formula (1) characterizes as follows：

R⁴Indicate the hydrocarbyl group with 12 to 24 carbon atoms；

W is number in the range of 0 to 10, preferably 0 to 3；

A ' O indicate the polyoxyalkylene group with 2 to 4 carbon atoms；And

R³Indicate alkyl with 1 to 4 carbon atoms group；

X indicates halogen, sulfate radical or carbonate；

P is number in the range of 1 to 10, preferably in the range of 1 to 5.

12. according to any method of the preceding claims, wherein the compound choosing such as provided in step b) The group of the compound composition of free style (1a)：

Wherein,

AO、p、t、x R¹、R²、R³With X as defined in claim 1, preferably as defined as claimed in claim 11.

13. according to the method for claim 12, wherein the compound of the formula (1a) characterizes as follows：

R¹It indicates with 1 to 20, preferably 1 to 10 carbon atom, preferably with 2 to 6 carbon atoms and more preferably has There is the alkylidene group of 4 carbon atoms；

R³Indicate the hydrocarbyl group with 1 to 4 carbon atom, the preferably alkyl group and more with 1 or 2 carbon atom Preferably methyl group；

AO is polyoxyalkylene group, preferably ethoxy group；

X is number in the range of 1 to 15, preferably in the range of 2 to 10 and more preferably in the range of 1 to 6；

P is number in the range of 1 to 15；And

T is 0 or 1, preferably 1.

14. method according to claim 12 or 13, wherein the compound of the formula (1a) possesses in following characteristics extremely It is one few：

R¹Derived from dicarboxylic acids, dicarboxylic acid chloride, the diester of dicarboxylic acids, dicarboxylic acids acid anhydrides, preferably R¹Derived from selected from by The compound of group consisting of：Oxalic acid, malonic acid, succinic acid, glutaric acid, glutaconate, adipic acid, muconic acid, pimelic acid, Phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, malic acid, maleic acid, fumaric acid, suberic acid, mesaconic acid, the last of the ten Heavenly stems two It is acid, azelaic acid, tartaric acid, itaconic acid, glutinicacid, citraconic acid, brassylic acid, dodecanedioic acid, traumatic acid, thapsic acid, right The methyl esters or ethyl ester or acid anhydrides of the acid chloride, these compounds answered and its mixture, more preferably R¹Derived from selected from The compound for the group being made up of：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, four Hydrogen phthalic acid, malic acid, tartaric acid, corresponding acid chloride, the methyl esters of these compounds or ethyl ester or acid anhydrides and Its mixture, and most preferably adipic acid；

R²Derived from the fatty amine selected from the group being made up of：2 ethyl hexylamine, 2- propyl heptyl amice, n-octyl amine, n-Decylamine, just Dodecyl amine, (Cocoalkyl)-amine, (palm oil alkyl) amine, n-tetradecane base amine, n-hexadecyl amine, n-octadecane base amine, Oleyl amine, (tallow alkyl)-amine, (hydrogenated tallow alkyl)-amine, (rapeseed alkyl)-amine, (soya alkyl)-amine, erucic amide, N- (positive decyl)-N- methyl-trimethylenes-diamines, N- (dodecyl)-N- methyl-trimethylenes-diamines, N- (cocounut oil alkane Base)-N- methyl-trimethylenes-diamines, N- (rapeseed alkyl)-N- methyl-trimethylenes-diamines, N- (soya alkyl)-N- Methyl-trimethylene-diamines, N- (tallow alkyl)-N- methyl-trimethylenes-diamines, N- (hydrogenated tallow alkyl)-N- methyl- Trimethylene-diamines, N- (erucic acid)-N- methyl-trimethylenes-diamines, isotridecyl oxygen propylamine and its mixture, preferably Ground (Cocoalkyl)-amine or (tallow alkyl)-amine；

R³Derived from the alkylating agent selected from the group being made up of：Dimethyl suflfate, dithyl sulfate, dimethyl carbonate, benzyl Chlorine, methyl bromide, methyl chloride, methyl iodide, preferably dimethyl suflfate or methyl chloride and its mixture.

15. method according to claim 12 or 13, wherein the compound of the formula (1a) possesses following characteristics：

R²Derived from the ethoxylated fatty amine selected from the group being made up of：Ethoxylation (C₁₆-C₁₈) and C₁₈Unsaturated alkyl Amine, ethoxylation (C₈-C₁₆) and C₁₈Unsaturated alkyl amine, ethoxylation (Cocoalkyl)-amine, ethoxylation oil base amine, ethoxy Base (tallow alkyl)-amine and ethoxylation (palm oil alkyl)-amine；And

R³Derived from the alkylating agent selected from the group being made up of：Dimethyl suflfate, dithyl sulfate and methyl chloride, and it is excellent Selection of land is methyl chloride.

16. according to any method of the preceding claims, the wherein collecting agent of step b) is by one or more Formula (1) or the compound of (1a) composition.

17. according to any method of the preceding claims, wherein the aqueous suspension obtained in step c) With 7 to 10, preferably 7.5 to 9.5 and more preferably 8.5 to 9.0 pH.

18. according to any method of the preceding claims, wherein to be caught described in amount below addition in step c) Receive agent：1 to 5 000ppm of the gross dry weight of the material containing white pigment and impurity based on step a), preferably amount are 20 to 2 000ppm of the gross dry weight of the material containing white pigment and impurity based on step a), more preferably amount is 30 To 1 000ppm, and most preferably amount is 50 to 800ppm.

19. according to any method of the preceding claims, wherein the aqueous suspension obtained in step c) Solid content between 5 weight % and 80 weight % with the total weight based on the solid in the suspension, based on described Between the preferably 10 weight % of the total weight of solid in suspension and 70 weight %, more preferably 20 weight % and 60 weights It measures between % and the most preferably solid content between 25 weight % and 55 weight %.

20. according to any method of the preceding claims, wherein before, during or after step c) by a kind of or Multiple additives are added to the aqueous suspension, wherein the additive is selected from the group being made up of：It is pH adjusting agent, molten Agent, inhibitor, polyelectrolyte, foaming agent and the collecting agent other than according to the collecting agent of formula (1) and/or (1a).

21. according to any method of the preceding claims, wherein the aqueous suspension obtained in step c) It mills during and/or after step c).

22. according to any method of the preceding claims, the gas wherein in step d) is air.

23. according to any method of the preceding claims, wherein the suspension in the step has at 5 DEG C With 40 DEG C between, preferably between 10 DEG C and 40 DEG C, more preferably between 10 DEG C and 30 DEG C and most preferably at 15 DEG C With the temperature between 25 DEG C.

24. according to any method of the preceding claims, wherein what is obtained from step e) is described with white pigment Phase disperseed and/or milled before or after step e), and preferably at least one dispersant and/or extremely Few one kind, which is milled, is disperseed in the presence of auxiliary agent and/or is milled.

25. can by the phase with white pigment described in obtaining according to any method of the preceding claims with Purposes in lower：Paper, plastics, paint, coating, concrete, cement, cosmetics, water process, food, pharmacy, ink and/or agriculture Industry application, wherein the product containing white pigment be preferably used for the wet-end process of paper machine, cigarette paper, cardboard and/or In coating application, or as rotogravure printing and/or offset printing and/or ink jet printing and/or continuous ink jet printing and/or aniline Printing and/or electrofax and/or ostentatious support.